New photochromic amorphous molecules containing core of triphenylamine and three branches of azobenzene were obtained in good yields by Pd-catalyzed amination. High glass temperature (Tg) above 100°C of these molecules was because of many triphenylamine units and high molecular weight. The stable amorphous films of these molecules could be easily prepared by spin-coated method. The photoinduced and thermal isomerization were observed in the amorphous films and the solutions. The size of the core had no clear effect on rates and activation energy values (Ea) of the cis→trans thermal isomerization in solution.