In this paper, we synthesized a new photo-crosslinkable polyitaconimide containing cinnamoyl moiety by radical polymerization. Also, the nematic liquid crystal (NLC) alignment capabilities on these photopolymer surfaces were studied. Good LC alignment with UV exposure on the polyitaconimide surfaces can be obtained. A homogenous alignment using UV exposure on the polyitaconimide with 1-carbon chain cinnamoyl group and 4-carbon chain cinnamoyl group can be obtained. However, a homeotropic alignment using UV exposure was observed on polyitaconimide with 6-carbon chain cinnamoyl. The LC aligning ability on the polyitaconimide depends on the side chain length of photopolymer.