Rigid long side-chain liquid crystalline polymers with intermolecular hydrogen bonds were synthesized with random styren-maleic anhydride copolymer(RSMA) and p-hydrobenzoic acid(HBA) by catalyzing and in-situ acetylation. Their chemical structures were characterized by FTIR spectrum, Polarizing microscope with hot-stage and DSC were applied to investigate the liquid crystallinity. It was found that RSMA-g-HBA copolymers contain intermolecular hydrogen bonds and exhibit nematic mesophase.