The mechanism of photo-induced liquid crystal (LC) alignment on a poly(vinyl cinnamate) (PVCi) thin layer was studied. By spectral analysis for the polarized UV spectra of the PVCi thin layer exposed to a polarized UV, dichroism of the photo-dimer and photo-isomer could be determined. To elucidate the mechanism of photo-induced LC alignment, changes in the dichroism of the photo-products and photoaligned LC were investigated with two successive irradiations of polarized UV (250-340 nm) with different polarization directions to the PVCi thin layer. The dichroism of the photoaligned LC was found to follow not the dichroism of the photo-isomer but that of the photo-dimer, which indicates that the anisotropic distribution of the photo-dimer is mainly responsible for uniform LC alignment.