The electro-optical (EO) performances for the twisted-nematic (TN)-liquid crystal display (LCD) photo-aligned with polarized UV exposure on various blending photopolymer surfaces were investigated. Excellent LC alignment and voltage-transmittance (V-T) characteristics for TN-LCD photo-aligned with polarized UV exposure of normal incidence on the blending photopolymer (polyimide (PI) +PM4Ch(poly(4-methacryloyloxy chalcone))) surface containing chalcone group can be achieved. The EO performances for the TN-LCD photo-aligned on the blending photopolymer can be improved due to the photosensitivity by long side chain of the photopolymer.