A series of rigid-rod poly(p-benzamide) polymers (PBA) with different length of flexible alkyl side chains, denoted as PBA(n)Cs, have been prepared by N-alkylation method. The alkyl side chain lengths varied from decyl (n = 10) to octadecyl (n = 18), with an interval of two carbon atoms. The packing mode and conformational transition of the alkyl side chains of the prepared PBA derivatives were characterized by wide-angle X-ray diffraction (WAXD), differential scanning calorimertry (DSC), and Fourier transform infrared spectroscopy (FTIR). WAXD results revealed that the derivatives form layered structure in which the distance between the backbones depends on the length of alkyl side chains. DSC studies indicated that melting transition temperature of PBA(n)Cs increases accordingly with increasing the alkyl chain length of the substituents. Meanwhile, DSC results proved that as the carbon atom number of the side group exceeds 14, alkyl side chains in PBA(n)Cs tend to crystallize FTIR spectroscopic investigation showed that the all-trans zigzag conformation is the most stable state for the alkyl side chain in PBA18C comb-like polymer. Temperature variation caused the reversible transition between trans and gauche conformational states of the side octadecyl group, and in turn made the molecular chain packing mode of PBA18C comb-like polymer undergo an reversible transformation from ordered packing to disordered packing. (C) 2004 Elsevier Ltd. All rights reserved.