A series of new luminescent and electrochromic polyimidothioethers (PITEs) was prepared from a new triphenylamine-based bismaleimide and commercial dithiols via Michael polyaddition. With organo-processability and high thermal stability, the optoelectronic properties of these PITEs were investigated and they demonstrated great potential as multifunctional materials for ambipolar electrochromic and electrofluorochromic devices, and fluorescent electrospun fibers.