X-ray diffraction analysis on C60 films shows that besides fcc phase, there also exists hcp phase, as well as a new crystalline phase with interplanar spacing (d-spacing) of planes parallel to the substrate 0.95 nm. The new phase may relate to the intercrystalline packed C60 molecules between fcc crystallites. The room temperature electrical conductivity of C60 films is found to be in the range of 10−5–10−8 (Ω · cm)−1. The room temperature conductivities of C60 films annealed at temperatures above 473 K are lower by one order of magnitude than those at temperatures below 463 K. This is because the interconnection between the fcc crystallites is weakened due to the disappearance of the new intercrystalline phase and the subsequent heightening of the intercrystalline potential barrier. From the measurement on the conductivity versus time when the film is maintained at a constant temperature, we identified the increase of conductivity is the result of the decrease of hcp phase, while the decrease of conductivity is due to the decrease of the new intercrystalline phase. Because the structures of the films become highly ordered, and defect states in the energy band gap decrease on annealing at high temperature, the conductivity activation energy increases.