Two series of novel polyamides I-II with diphenylamine (DPA) and triphenylamine (TPA)-derivatives were prepared via the low temperature polycondensation from two kinds of synthesized diamines and diacid chlorides, respectively. The aromatic polyamides had useful level of thermal stability associated with relatively high glass-transition temperatures (Tg) (252–275°C), 10% weight-loss temperatures (Td10) nearly in excess of 430°C, and char yield at 800°C in nitrogen higher than 55%. Due to the additional 4-methoxy-phenyl ring which can provide additional route to stabilize the cation radical formed during oxidation, the TPA-based polyamides III revealed more stable electrochemical oxidation behavior and better electrochromic reversibility than DPA-based polyamides. In addition, the prepared electrochromic films had high coloration efficiency, low switching time, and good redox stability.