In this study, Nb-Cr binary mixtures were prepared by mechanical alloying. And mechanical alloying process of mixed Nb-Cr(1:2) powders was studied, and the phases of milling powders analyzed by XRD and SEM. It has been found that the powders form solid solution first, then amorphous phase appeared gradually and crystallization of amorphous takes place with the different milling time. A thermodynamic model of MA of Nb-Cr system was developed based on Miedema Semi-experimental theory to explain the phase transformations of Nb-Cr system during milling. Using Miedema semi-empirical model the free energies of the ordered Laves-phase NbCr2 intermetallics, solid solution and amorphous alloy were calculated. From XRD and SEM analysis of Nb/2Cr powders prepared by mechanical alloying in a planetary ball milling, it was found that the calculated results were in accordance with the experiments.