Abstract: In this research, triphenylamine (TPA) and 4,4′-dimethoxytriphenylamine (TPAOMe), were successfully linked with two high performance AIEgens, triphenylethylene (TPE) and benzo[b]thiophene 1,1-dioxide (BTO), to obtain four AIE/electro-active materials, TPETPA, BTOTPA, TPETPAOMe and BTOTPAOMe, respectively. These materials were used to fabricate gel-type electrochromic devices (ECDs), and the effects of AIE-active pendent groups on photoluminescent (PL) characteristics, EC and electrofluorochromic (EFC) behaviors were further investigated. The PL performance of the obtained materials in the solution, aggregated and solid states were obviously influenced by the different substituents. Furthermore, TPETPAOMe and BTOTPAOMe derived from TPAOMes revealed enhanced AIE performance, higher electrochemical stability after 500 cycle cyclic voltammetry scan when compared with the corresponding ones derived from TPAs without methoxy moieties. Subsequently, these two methoxy-substituted AIE/electro-active materials were utilized for fabricating high-performance EFC devices. The obtained devices exhibited strong emitting capability under UV irradiation at neutral state, and the emission could be quenched effectively during electrochemical oxidation procedure. In addition, we further introduced a well-known cathodic material, heptyl viologen (HV), into the EFC devices to obtain an ambipolar system, and the resulted devices demonstrated enhancing EC properties including lower working potential, faster switching time and reversibility owing to the ion storage effect between TPA-based materials and HV. Keywords: triphenylamine, triphenylethylene, benzo[b]thiophene 1,1-dioxide, AIE, electrofluorochromism