Poly(amide-imide)s(PAIs) with different microstructures were prepared based on trimellitimide and 4,4'-diphenylether with varying the reaction conditions. The microstructures of PAIs were examined by 500 MHz H-1-NMR spectroscopy. The head-to tail (HT-) PAI showed a sharp peak in WAXD curve, a large shift at around 1670 cm(-1) for -C=O stretching in FT-LR spectra, and poor solubility in organic solvents, high density, Tg, tensile strength and modulus compared to head-to-head (HH-) PAI and copolymers of HT and HH. These results might be due to the higher packing tendency of the HT PAI than HH PAI or copolymers.