The molecular orientation-photoconductivity relationships of several kinds of phthalocyanine polymer (PPc)-oriented thin films have been studied in double-layered photoreceptor devices, where the charge-generation layers (CGLs) are phthalocyanine polymer-oriented thin films and the charge-transportation layers (CTLs) are composed of hole transporting materials of tetraphenyl benzidine or hydrazone. The oriented thin films containing PPc dispersed in polyvinyl difluoride (PVDF) were prepared by the electric field orientation. The results showed that the photosensitivities of the phthalocyanine polymer (PPcs)-oriented thin films were higher than those of the unoriented PPcs thin films, and varied with their molecular structures and the molecular stacking in the films. This was thought to be due to the molecular orientation effect, which was demonstrated by the analyses of the polarized fluorescence, DSC, FTIR reflection absorption spectroscopy (FTIR-RAS), and angle-dependent XPS.