The new phto-alignment material PMI5CA, poly{N-(phenyl)maleimide-co-3-[4-(pentyloxy) cinamate]porpyl-2-hydroxy-1-methacrylate}, was synthesized and the electro-optical (EO)characteristics in the vertical-aligned(VA) liquid crystal display (LCD) photo-aligned on the photopolymer surface were studied. Excellent Voltage-transmittance(V-T) characteristics in the VA-LCD photoaligned with polarized UV exposure of oblique direction on the pohotopolymer surface for 1 min can be achieve. The transmittance of the VA-LCD photoaligned on the photopolymer surface decreased with increasing UV exposure time. We suggest that decrease of transmittance in the VA-LCD photoaligned on the photopolymer surface is attributed to the dissociation of the ester linkage in the photodimerized cinnamate structure with increasing UV exposure time.