New photh-alignment materials based on PCEMA (poly(4-methacryloyloxylchalcone))for liquid crystal (LC) aligning were synthesized. and the electro(EO) characteristics of the photo-aligned TN-LCD were investigated. The excellent LC alignment and voltage-transmittance (V-T) characteristics for the photo-aligned TN-LCD on PCEMA surface containing more cinnamoly group can be achieved. However the reverse tilt disclinations for the photo-aligned TN-LCD on the PCEMA surface containing more OH group were observed. Consequently we suggest that the LC aligning capabilities can be increased by increasing of cinnamoly group on the PCEMA surfaces.