Three bis(dimethoxytriphenylamine)-diimides, OMeTPA-PMDI, OMeTPA-NTDI, OMeTPA-PTDI, and three bis(di-tert-butyltriphenylamine)-diimides, tBuTPA-PMDI, tBuTPA-NTDI, tBuTPA-PTDI, were synthesized from condensation of 4-amino-4’4”-dimethoxytriphenylamine and 4-amino-4’4”-di-tert-butyltriphenylamine with pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and 3,4,9,10-perylenetetracarboxylic dianhydride (PTDA), respectively. All the TPA-diimide compounds were electrochemically active and undergo reversible oxidation and reduction as evidenced by cyclic voltammetry. These diimide compounds exhibited ambipolar multi-colored electrochromism with good switching stability and high coloration efficiency during both anodic and cathodic scanning. Incorporation of methoxy or tert-butyl substituents on the TPA active sites reduces oxidation potentials and increases redox stability of these TPA-diimides. The electrochromic devices using these diimides as electroactive compounds displayed reliable electrochromic performance.