We synthesized the two types of photoalignment material of high thermal resistance with hydroxyl aromatic polyimide, and studied the liquid crystal (LC) aligning capabilities on the photopolymer layers. Also, electro-optical (EO) performances for the twisted-nematic (TN)-liquid crystal display (LCD) photoaligned with linearly polarized UV exposure were investigated. A good LC alignment with UV exposure on the two types of photopolymer surface can be obtained. The Voltage-transmittance (V-T) curve in the photoaligned TN cell with UV exposure was different from two type. The response time of photoaligned TN cell was measured about 21 ms in two alkyl chain and about 15 ms in four alkyl chain.