Crystalline MoS2 films were deposited on Si and graphite substrates using MoF6 and H2S as precursors. The crystal orientation and near-interface structure of the MoS2 films were studied using transmission electron microscopy. In general, the preferred orientation of the (002) basal planes of the MoS2 films with respect to the substrate surface changed from parallel to perpendicular with increased deposition temperature from 320 to 430 °C. At 430 °C, the basal planes were primarily oriented perpendicular to the Si substrate, except for the presence of a ∼5 nm interface region in which the basal planes were oriented in the parallel direction. The formation of this transitional region was also observed on the graphite substrate.