A series of novel liquid crystal were synthesized with alkyloxyben- zimidoylbenzoic acid (CnABOH) and poly(4-binylpridind) (PVP) through hydrogen bond self-assemble between carboxyl groups of alkyloxybenzimidoylbenzoic and nitrogen of PVP. PVP was used as a hydrogen bond acceptor polymer. The CnABOH (n is the number of carbon atom) had been used as H-bond donor. The existence of H-bond was confirmed used FTIR spectroscopy. Optical microscopy was used to investigate liquid crystalline behaviors. The mesophases of the complexes (PVP-CnABOH) were obviously different from LC behaviors of the CnABOH. With increasing length of terminal group, the melting temperature reduced and the temperature range of the LC mesophase increased. For instance, while the number of carbon atom increased from 3 to 8, the melting temperature reduced from 180°C to 156°C and the range of LC mesophase increased from 36°C to 84°C.