Geopolymers are a relatively new class of materials that have many broad applications, including use as substitute for ordinary Portland cement (OPC), use in soil stabilisation, fire resistant panels, refractory cements, and inorganic adhesives. Geopolymers are an alternative binder to Portland cement in the manufacture of mortars and concrete, as its three-dimensional alumino silicate network develops excellent strength properties. Use of geopolymers in place of ordinary Portland cement is also favoured owing to the possible energy and carbon dioxide savings. Geopolymer is typically synthesized by alkali activation of pozzolanas at moderate temperatures (< 1000C). The focus of the thesis is synthesis and characterization of geopolymers as construction materials. In this context, the role of compositional factors, such as, pozzolana type (fly ash, kaolinite, metakaolinite, ground granulated blast furnace slag, red soil), alkali (sodium hydroxide is used in this study) activator concentration, Si/Al (Si= silicon, Al = aluminium) ratio of the pozzolana and environmental factors, namely, curing period and temperature are examined. Besides synthesizing geopolymers that could be an alternate to concrete as construction material, sand-sized aggregates were synthesized using geopolymer reactions. This was done as river sand is becoming scarcer commodity for use as construction material. Several compositional and environmental factors were varied in geopolymer synthesis in order to identify the optimum synthesis conditions that yield geopolymers with maximum compressive strength. Besides varying external (compositional and environmental) factors, the role of internal microstructure in influencing the compressive strength of the geopolymer was examined. Micro-structure examinations were made using X-ray diffraction (XRD), scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) studies. The studies on compositional and environmental factors in geopolymer synthesis brought out several interesting results. The results firstly brought out that amongst the pozzolanas studied, ASTM class F fly ash is most suited for maximum compressive strength mobilization upon geopolymer reactions. Moderate temperature (75-1000C) was adequate to mobilize large compressive strengths. Room temperature curing needed more than 7 days before the pozzolana-NaOH paste began to develop strength. Curing period of 56 days was needed for the geopolymer to develop significant strength (19.6MPa). A similar range of compressive strength could be developed by the pozzolana-NaOH paste upon curing for 3 days at 1000C. Likewise curing the pozzolana-NaOH paste at temperatures > 1000C led to reduction in compressive strength from shrinkage and breakage of bonds. A caustic soda (NaOH) concentration of 10 M was adequate to develop maximum compressive strength of the geopolymer. Caustic soda concentrations in excess of 10 M did not result in further improvement of strength. The Si/Al ratio also contributes to strength mobilization. The Si/Al ratio of the geopolymer was enhanced by mixing commercially obtained silica gel with the pozzolana. Maximum strength mobilization was observed at Si/Al ratio = 2.45 corresponding to 6.5 % silica gel addition to the pozzolana (on dry mass basis). Comparing compressive strengths of geopolymers with varying silica gel contents, geopolymer specimens with least water content and largest dry density did not exhibit maximum compressive strength indicating that the physico-chemical (bond strength, micro-structure) played a pivotal role than physical parameters (dry density, water content) in dictating the strength of the geopolymer. MIP results showed that bulk of the porosity in fly ash geopolymer specimens is contributed by macro pores and air voids. Geopolymerization leads to bulk consumption of cenospheres in fly ash and forms polymerized matrix with network of large pores. After geopolymerization, all the main characteristic peaks of Al–Si minerals observed in fly ash persisted, suggesting that no new major crystalline phases were formed. Presence of small amount of inorganic contaminants in fly ash can drastically reduce the strength of the fly ash geopolymer. For example, 5-20 % presence of red soil reduces the strength of fly ash geopolymer by 16 to 59 %. Presence of unreacted clay coupled with less porous structure is responsible for the reduction in compressive strength of fly ash geopolymer subjected to red soil addition. MIP studies with geopolymers also revealed that there is good bearing between compressive strengths and maximum intruded volume (from MIP test) of geopolymers. For example, fly ash geopolymer specimen exhibits highest total intruded volume (0.3908 cc/g) and largest compressive strength of 29.5 MPa, while red soil geopolymer specimen exhibit least intruded volume (0.0416 cc/g) and lowest compressive strength (5.4 MPa). Further, analysis showed that specimens with larger airvoids+macropores volume had larger compressive strength, suggesting that geopolymers with more porous microstructure develop larger compressive strength. All geopolymer specimens exhibited tri-modal nature of pores i.e. macro-pore mode (entrance pore radius: 25-5000 nm), mesopore mode (entrance pore radius: 1.25 to 25 nm) and air void mode (entrance pore radius >5000 nm). The micro pores (entrance pore radius < 1.25 nm) do not contribute to porosity of the geopolymer specimens. Sand particles prepared from geopolymer reactions (FAPS or fly ash geopolymer sand) predominated in medium sized (2mm to 0.425 mm) sand particles. Their particle size distribution characteristics (uniformity coefficient and coefficient of curvature) classified them as poorly graded sand (SP). Dissolution, followed by polymerization reactions led to dense packing of the Si–O–Al–O– units that imparted specific gravity of 2.59 to FAPS particles which is comparable to that of river sand (2.61). Dissolution in strongly alkaline medium imparted strongly alkaline pH (12.5) to the FAPS particles. The river sand is characterized by much lower pH (7.9). Despite being characterized by rounded grains, the FAPS particles mobilized relatively high friction angle of (35.5o) than river sand (∅ = 28.9o). The river sand-mortar (RS-M) and fly ash geopolymer sand-mortar (FAPS-M) specimens developed similar 28-day compressive strengths, 11.6 to 12.2 MPa. Despite its higher water content, FAPS-mortar specimens developed similar compressive strength and initial tangent modulus (ITM) as river sand-mortar specimens. The FAPS-M specimen is more porous (larger intruded volume) with presence of larger fraction of coarser pores. Total porosity is majorly contributed by macro-pores (67.92%) in FAPS-M specimen in comparison to RS-M specimen (macro-pores = 33.1%). Mortar specimens prepared from FAPS and river sand exhibit similar pH of 12.36 and 12.4 respectively. FAPS-mortar specimens have lower TDS (1545 mg/L) than river sand-mortar specimens (TDS = 1889 mg/L). The RS-M and FAPS-M specimens exhibit leachable sodium levels of 0.001 g Na/g RS-M and 0.007 g Na/g-FAPS-M respectively in the water leach tests. The larger leachable sodium of FAPS-M specimen is attributed to residual sodium hydroxide persisting in the FAPS even after washing. The ultra-accelerated mortar bar test (UAMBT) shows that the percentage expansion of FAPS-M and RS-M specimens are comparable and range between 0.07 to 0.08 %.