Titanium alloys are important engineering alloys that are extensively used in various industries. This is due to their unique combination of mechanical and physical properties such as low density combined with high strength and toughness as well as outstanding corrosion resistance. An additional benefit associated with Ti alloys, in general, is that their properties are relatively temperature-insensitive between cryogenic temperature and ~500 °C. Amongst the Ti alloys, Ti-6Al-4V (referred as Ti64) is a widely used alloy. Conventionally cast Ti64 possesses classical Widmanstätten microstructure of (hcp) α and (bcc) β phases. However this microstructure suffers from large prior β grain size, which tends be in the order of a few mm. Such large grain sizes are associated with poor processability as well as inferior mechanical performance. The necessity to break this coarse as-cast microstructure down, through several successive thermo-mechanical processing steps, adds considerably to the cost of finished Ti alloy products, making them expensive vis-à-vis other competing alloys. The addition of small amount of B (~0.1%) to Ti64 alloys, on the other hand reduces the cast grain size from couple of mm to ~200 µm. Moreover, addition of B to Ti alloys produces the intermetallic TiB needles during solidification by an in situ chemical reaction. The overall objective of this work is to gain insights into the role of microstructural modifications, induced by B addition to Ti64, on the mechanical performance of the alloys, in particular the room temperature damage tolerance (fracture toughness and fatigue crack growth) characteristics. The key questions we seek to answer through this study are the following: (a) What role does the microstructural refinement plays on the quasistatic as well as fracture and fatigue behavior and high temperature deformability of the alloys? (c) A hierarchy of microstructural length scales exist in Ti alloys. These are the lath, colony and grain sizes. Which of these microstructural parameters control the mechanical performance of the alloy? (b) What (possibly detrimental) role, if any, do the TiB needles play in influencing the mechanical performance of Ti64 alloys? This is because TiB being much stiffer, strain incompatibility between the matrix and the TiB phase could lead to easy nucleation of cracks during cyclic loading as well as can pose problems during dynamic deformation. (d) What is the optimum amount of B that can be added to Ti64 such that the most desirable combination of properties can be achieved? Five B-modified Ti64 alloys with B content varying from 0.0 to 0.55 wt.% were utilised to answer the above questions. Marked prior β grain size reduction was noted with up to 0.1 wt.% B addition. Simultaneous refinement of α/β colony size has also been observed. The addition of B to Ti64, on the other hand increases the α lath size. The TiB needles that form in-situ during casting are arranged in a necklace like structure surrounding the grain boundaries for higher B added Ti64 alloys. An anomalous enhancement in elastic modulus, E, of the alloy with only 0.04 wt.% B to Ti64 was found. E has been found to follow the same trend of variation with B content at higher temperatures (up to 600 °C) as well. Nanoindentation experiments were conducted to evaluate the moduli of the various phases present in the microstructure and then rationalize the experimental trends within the framework of approximate models. Marginal but continuous enhancement in strength of the alloys with B addition was observed. It correlates well with the grain size refinement according to Hall-Petch relationship. Ductility on the other hand increases initially with up to 0.1 wt.% B addition followed by a reduction. While the former is due to the microstructural refinement, the latter is due to the presence of significant amount of brittle TiB phase. Room temperature fracture toughness decreases with B addition to Ti64. Such reduction in fracture toughness with the refinement of prior β grain size has been justified with Ritchie-Knott-Rice model. Contradictory roles of microstructural refinement have been observed for notched and un-notched fatigue. While reduction in length scale has a negative role in crack propagation, it enhances the fatigue strength of the alloy owing to better resistance to fatigue crack initiation. TiB needles on the other hand act as sites for crack initiation and hence limit the enhancement in fatigue strength of alloys with 0.30 and 0.55 wt.% B. An investigation of the high temperature deformability of the alloys has been performed over a wide range of temperature (within the two phase α+β regime) and strain rate windows. Results show that microstructural refinement does not alter the high temperature deformation characteristics as well as optimum processing conditions of the alloys. TiB needles, however act as sites for instability owing to differences in compressibility between the matrix and the whisker phase. In summary, this study suggests that the addition of ~0.1 wt.% B to Ti64 can lead to the elimination of certain thermo-mechanical processing steps that are otherwise necessary for breaking the as-cast structure down and hence make finished Ti components more affordable. In addition, it leads to marginal enhancement in the quasi-static properties and significant benefits in terms of high cycle fatigue performance.