The glass-forming composition ranges in Al-La-Ni and Mg-TM (Cu, Zn)-Y alloys were predicted using Miedema’s model. Glass-forming abilities of Al-La-Ni alloys and Mg-Cu-RE alloys were studied in terms of reduced glass transition temperature (Trg), supercooled liquid region (∆Tx) and γ parameters. The glass-forming ability parameters of Mg-Cu-RE (RE: rare-earth) alloys were correlated with Mendeleev number. The Miedema model has been used to determine glass-forming composition range in binary Al-La, Al-Ni and La-Ni alloy systems and the ternary Al-La-Ni system by neglecting the ternary interactions. The glass-forming composition range for Al-La, Al-Ni and La-Ni alloy systems extends from 5 to 90 at% La, 30 to 80 at% Ni and 5 to 95 at% Ni, respectively. In these systems the predicted glass-forming composition range is wider than the experimentally observed range. Miedema model, restricting the difference of enthalpy of formation between the amorphous and solid solution phases to within –10000 J/mole to –55000 J/mole gives rise to better prediction of glass-forming composition range compared to the original models. The concept of mixing enthalpy and mismatch entropy has been used in order to quantify Inoue’s criteria of glass formation. The mixing enthalpy and normalised mismatch entropy of the ternary Al-La-Ni alloys, calculated by the extended regular solution model, vary between –12 to –40 kJ/mol and 0.16 to 0.65, respectively. The enthalpy contour plot has been constructed to distinguish the glass-forming compositions on the basis of the increasing negative enthalpy of the composition. Six Al rich Al-La-Ni alloys with nominal compositions Al89La6Ni5, Al85La10Ni5, Al85La5Ni10, Al82La8Ni10, Al80La10Ni10 and Al60La20Ni20 three La rich Al-La-Ni alloys with nominal compositions Al34La33Ni33, Al40La40Ni20 and Al25La50Ni25 have been chosen from the Al-La-Ni ternary phase diagram, to study the glass-forming ability of Al-La-Ni ternary alloy system and the correlation between La-based and Al-based glasses. All the alloys have been prepared using arc melting unit. All the alloy ribbons have been prepared using single-wheel vacuum melt-spinning unit. Two different wheel speeds of 20 m/s and 40 m/s were used for preparing ribbons of all the nine alloys. All the Al-La-Ni compositions, excluding equi-atomic composition (Al34La33Ni33) and Al60La20Ni20, give rise to amorphous phases. The supercooled liquid region and reduced glass transition temperature of this system increases with a decrease in Al content and an increase in La content. The glass-forming ability of the Al rich Al-La-Ni alloys is lower than that of the La-rich Al-La-Ni alloys. The glass-forming ability has been explained by taking into account the binary heat of mixing and the atomic radius mismatch of the constituent elements. Preferential crystallisation takes place during the heat treatment of glassy ribbons. The crystalline products are partially influenced by composition and binary heat of mixing between elements. Mg65Cu25Y10 alloy is a classical glass former of a family of Mg-based alloys. The partial or complete substitution of Y with other rare earth elements has been introduced to correlate the Mendeleev Number with the glass-forming ability parameters: reduced glass transition temperatures (Trg = Tg/Tl), supercooled liquid regions (∆Tx = Tx – Tg) and γ-criterion (TX/(Tg + Tm)). Mg-Cu-RE alloys with nominal compositions Mg65Cu25Y10, Mg65Cu25Y5Gd5, Mg65Cu25Y5Nd5, Mg65Cu25Gd10 and Mg65Cu25Nd10 were chosen for this work. The high reduced glass transition temperature, wider supercooled liquid region and higher γ value of Mg-Cu-Gd-Y amorphous alloy compared to Mg-Cu-Y and Mg-Cu-Nd-Y systems indicates that Mg-Cu-Gd-Y alloys possess higher glass-forming ability. The devitrification of all Mg-Cu-RE glassy alloys used for this work give rise to Mg2Cu (oF48) phase, which is known as anti-Laves phase. The glass-forming composition range for binary and ternary Mg-Cu-Y systems was calculated using Miedema’s model. The development of accurate methods of prediction of glass-forming ability in metallic systems is an important challenge. Pettifor has pioneered the Structure Mapping approach to binary intermetallics. The Pettifor approach can be adapted to the designing of bulk metallic glasses (BMGs). This method has been used to design Al-based and Mg-based BMG’s. Pettifor introduced an integer parameter to characterize the elements, which he called the Mendeleev Number. Essentially, Pettifor’s scheme orders the elements in a sequence of increasing electronegativity. With respect to Mendeleev Number, the Mg-Cu-RE system can be regarded as a binary system, because of the closeness of Mg and Cu (Mg:73, Cu:72, Y:25, Gd:27 and Nd:30). For this system, Mendeleev Number is a more effective parameter than atomic size (Mg: 1.60 Å, Cu: 1.27 Å), as a predictor of glass-forming ability. The effect of Y and rare earth elements on glass forming ability is similar. The atomic number of Y (39) is away from that of the rare earth elements and the Mendeleev Number of Y (25) comes in between those of the rare earth elements. Mg-Zn-Y system is an interesting system for researchers because of higher strength of these alloys. This system draws the crystallographers’ attention due to its composition-dependent structure variations. The Mg-rich RS/PM Mg-Zn-Y alloys yield superior mechanical properties. Therefore, the Mg-rich Mg-Zn-Y system has been chosen to study the microstructural evolution, even though the theoretical calculations for the glass-forming composition range for the Mg-Zn-Y system shows that this system is not a good glass former. Mg-Zn-Y system with nominal compositions Mg97Zn1Y2, Mg97Zn2Y1, Mg97−xZn1Y2Zrx and Mg92Zn6.5Y1.5 were chosen to study the microstructural evolution of these alloys. A small increase in Zn amount (above 2 at.%) in Mg-rich Mg-Y system results in quasicrystalline particles embedded in the matrix, whereas the addition of Zn up to 2 at.% leads to microstructural changes in the α-Mg solid solution.