•A new diimide-diacid with carbazole-substituted triphenylamine unit monomer was prepared.•PAIs with carbazole-substituted triphenylamine units were prepared.•These polymers showed good solubility and thermal stability.•PAI-7a shows good electrochemical properties, and optical contrast.A new carbazole-derived triphenylamine-containing diimide-diacid monomer (5), 4,4′-bis(trimellitimido)-4″-N-carbazolytriphenylamine, is prepared by the condensation of 4,4′-diamino-4″-N-carbazolytriphenylamine (4) and two molar equivalents of trimellitic anhydride (TMA). A series of new poly(amide-imide)s (PAIs) 7a–7d with carbazole-substituted triphenylamine units are prepared by direct polymerization from the new diimide-diacid (5) and various aromatic diamines (6a–6d). The PAIs shows high glass transition temperature between 269 and 297 °C, and high 5% weight loss temperature between 526 and 561 °C under nitrogen environment. Cyclic voltammograms of the PAIs films, which are casted onto the indium–tin oxide (ITO)-coated glass substrate, exhibit two reversible oxidation redox couples at 1.05–1.08 V and 1.38–1.46 V under an anodic sweep. The PAI-7a film reveals excellent stability of electrochromic characteristics for the radical cations generated, changing color from original pale yellowish neutral form to the green and then to dark blue oxidized forms. Furthermore, the anodically coloring of PAI-7a shows high coloration efficiency (CE = 205 cm2/C), high contrast of optical transmittance change (ΔT = 80% at 776 nm) and long-term redox reversibility.Graphical abstractA series of new poly(amide-imide)s (PAIs) with carbazole-substituted triphenylamine units were prepared by direct polymerization from the new diimide-diacid and various aromatic diamines. The PAI-7a film possesses excellent stability of electrochromic characteristics for the radical cations generated, changing color from original pale yellowish neutral form to the green and then to dark blue oxidized forms. Furthermore, the anodically coloring of PAI-7a shows high coloration efficiency (CE = 205 cm2/C), high contrast of optical transmittance change (ΔT = 80% at 776 nm) and long-term redox reversibility.