Titanium silicides prepared by codeposition at intermediate substrate temperatures with subsequent high temperature annealing were studied. It was found that coevaporation with Si/Ti ratio of 2.5 at the substrate temperature (Ts) of 120 °C results in the formation of an amorphous phase. On the other hand, samples prepared atTsof 300 °C resulted in crystalline TiSi2(C49). However, the amorphous phase was still present at the silicide/substrate interface. Considerable grain growth was observed to start at the silicide/Si interface even though the interfacial amorphous phase was the last to crystallize. It was suggested that Si diffusion is much more rapid through the amorphous silicide than crystalline TiSi2. This difference in kinetics was shown successful in explaining the dependency of the film properties of annealed samples on the structure of the product of the initial reaction.