Abstract: A new polymer containing triphenylamine in main chain was synthesized by polyaddition between 4 tert butyltriphenylamine and 1,3 diisopropenylbenzene. Effects of reactive temperature, catalyst concentration and monomer concentration on molar mass and yield were discussed. The resulting polymer exhibits high glass transition temperature and electroactivity. Results of UV spectrum and cyclic voltammography showed that the introduction of triphenylamine into polymer main chain did not affect its optical and electrochemical properties so much, indicating that the polymer is a promising hole transport material. The synthetic route can also be applied to the preparaion of other polymers containing triphenylamine.