Ordered poly(amide-thioether) (17) was prepared by tandem type polymerization of 2,4-dichlorophenyl acrylate (11), 4,4'-thiobis(benznenthiol) (12), and 4,4'-oxydianiline (16). The polymerization was carried out by mixing all monomers in the presence of catalytic amounts of triethylamine (TEA) and 1-hydroxybenzotriazole (HOBt) in 1-methyl-2-pyrrolidinone (NMP) at 20 degreesC for 2 h and then 80 degreesC for 2 days, yielding polymer 17 with a number-average molecular weight (M.) of 25 000. Authentic ordered poly(amide-thioether) (18) was prepared to verify the structure of polymer 17. The microstructure of polymers obtained was investigated by H-1 and C-13 NMR spectroscopy, and it has been found the polymer obtained has the expected ordered structure. Furthermore, model reactions were studied in detail to demonstrate the feasibility of ordered polymer formation.