The ordered [head-to-head (H-H) or tail-to-tail (T-T)] poly(amide-ester) was prepared by polycondensation of a symmetric monomer, isophthaloyl chloride (1), with 4-(2-aminoethyl)phenol (2) as a nonsymmetric monomer. The polymerization was conducted in NMP in the presence of triethylamine (TEA) at -20 degrees C by slow addition of 1 to 2, giving the ordered H-H or T-T poly(amide-ester) with an inherent viscosity of 0.27 dL/g, measured at a concentration of 0.5 g/dL at 30 degrees C in NMP. The authentic H-H or T-T, H-T ordered and random poly(amide-ester)s were prepared to verify the structure of ordered polymers. The microstructure of polymers obtained was investigated by H-1 and C-13 NMR spectroscopy, and it was found that the polymer obtained by polycondensation had the expected H-H or T-T ordered structure. Furthermore, the model reactions were studied in detail to demonstrate the feasibility of polymer formation. The constitutional regularity of polymers influenced the solubility, thermal properties, and crystallinity.