Niobium-Silicon alloys offer potential as a new generation of refractory material system that could meet the high-temperature capability envisaged to exceed the application temperatures of Ni base superalloys. A serious concern in the application of Nb based alloys is their poor oxidation resistance at elevated temperatures. The ternary diagram Nb-Ti-Si system exhibits eutectic groves nearly parallel to the Nb-Ti binary and terminate in a Class II invariant reaction, L+(Nb,Ti)3Si → β+ (Ti,Nb)5Si3. A peretectic ridge from the reaction, L+(Nb,Ti)5Si3 →(Nb,Ti)3Si also exists and these reactions control the microstructures resulting from solidification of these Nb alloys. The microstructures associated with these alloys comprise a distribution of Nb5Si3 in β matrix. The effect of various alloying elements on the resulting microstructures are illustrated The effect of microstructural distribution on oxidation resistance of multiphase alloys are also discussed.