Two series of new organosoluble polyamides with methyl-substituted triphenylamine (MeTPA) units showing anodically electrochromic characteristic were prepared from the phosphorylation polyamidation reaction of two diamine monomers, 4,4'-diamino-2 '',4 '',6 ''-trimethyltriphenylamine (Me(3)TPA-diamine; 2) and 4,4'-diamino-4 ''-methyltriphenylamine (MeTPA-diamine; 20), with various dicarboxylic acids, respectively. These polymers were readily soluble in many polar solvents and showed useful levels of thermal stability associated with relatively high glass-transition temperatures (T-g) (314-329 degrees C) and high char yields (higher than 62% at 800 degrees C in nitrogen). In addition, the polymer films showed reversible electrochemical oxidation, high coloration efficiency (CE), low switching time, and anodic green electrochromic behavior. The unexpected electrochemical behavior of higher oxidation potential and lower electrochemical stability of Me(3)TPA-polyamides I than MeTPA corresponding polymers could be attributed to the higher steric hindrance of ortho-substituents in Me(3)TPA moieties, thus made the resonance stabilization of cation radical much more difficult for the Me-3-substituted phenyl ring. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5271-5281, 2010