An aliphatic amino and an aliphatic hydroxyl group have been incorporated via Henry reaction highly efficiently toward the synthesis of a novel asymmetric aliphatic-aromatic diamine 2-amino-1-[4-(5-aminopyridyloxy)phenyl]-1-ethanol (AAP(y)P(h)E) in three steps. AAP(y)P(h)E shows good copolymerization reactivity with 4,4-oxydianiline (ODA) toward different aromatic dianhydrides, especially 4,4-oxydiphthalic anhydride (ODPA). TGA measurement and mechanical test results show that all polymers maintain the inherent thermal performance and tensile properties, while the glass transition temperatures (T-g's) by DMA show moderate decrease ranging from 185.5 to 253.3 degrees C due to the presence of aliphatic segments. The introduction of AAP(y)P(h)E is found to improve the solubility of the polymers, and the polymer films' optical transparency with decreased cutoff wavelength ((0)) ranging from 328 to 370 nm. Comparative studies reveal that the pendent aliphatic hydroxyls in the polymer chains would lead to interchain cross-linking via condensation and secondary weak cross-linking by hydrogen bond depending on different loading of AAP(y)P(h)E, which result in a fluctuation of hydrophilic-hydrophobic properties, DMA tan and dielectric constant of the copolymer films. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3413-3423