The solid state reaction of Mo/Si multilayer thin films produced by RF magnetron sputtering technique was examine dusing differential scanning calorimetry (DSC) and x-ray diffraction, and explained in view of two concepts, effective drivig force and effective heat of formation. In constant scanning rate DSC, there were two exothermic peks which corresponded to the formation of h-MoSi2 and t-MoSi2 , respectively. The activation energyfor theformation of h-MoSi2 was 1.5eV , and that of t-MoSi2 was 7.8eV. Nucleation wa stherate controlling mechanism for each of the silicide formation. Amorphous phase was not formed , which was consistent withtheprediction by the concept of effective driving force. h-MoSi2 the first crystalline phase, was considered to have lower interfacial free energy than t-MoSi2 and by increasing temperature it was transformed into more stable t-MoSi2.