The formation of TiSi2 thin films on Si has been investigated by in situ x-ray diffraction and by electrical transport. The x-ray results show unequivocally that the staging proceeds through two orthorhombic polytypes of TiSi2 according to the sequence: sputter-deposited metallic Ti films on Si (001) → TiSi2 (C49 structure) → TiSi2 (C54 structure), with no evidence of lower suicides. Electrical transport shows metallic behavior for all phases and distinctive features in the annealing curves which correlate with the structural transformations. Most importantly, the resistivity, characteristically very high for the C49 phase, undergoes a precipitous drop at the C49 → C54 transition. Total energies for both phases are calculated and, consistent with the occurrence of a structural phase transformation, are found not to differ appreciably.