Aromatic moieties of benzene and pyridine as side chains for poly(thiophene-3-yl-amine) are rationally designed and synthesized by facile self acid-assisted polycondensation (SAAP). Nitrogen atom is the key atom to form ammonium cation which guarantees SAAP success while other aromatic moieties are chosen carefully to attach on N atom to functionalize poly(thiophene-3-yl-amine) matrix. Our results indicate that thiophene-3-yl-amine is an excellent platform to construct plenty of functionalized monomers candidates for SAAP. Our study would push SAAP or AAP scope forward and pave the way to explore much more polythiophene derivatives. Furthermore, DFT calculation is carried out to deep understand AAP mechanism. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 4003-4012