A novel electrochromism (EC) and photoluminescence (PL)-active poly(4-cyanotriphenylamine) (CN-PTPA) is prepared by oxidative coupling polymerization from 4-cyanotriphenylamine (CN-TPA) using FeCl3 as an oxidant. The high-performance electrofluorochromic (EFC) devices using CN-PTPA thin film with photoluminescent quantum yield of 21.9% as active layer are readily fabricated and reveal the highest fluorescent contrast ratio (I-off/I-on) of 242 between the fluorescent (neutral) state and the non-fluorescent (oxidized) state, rapid response time shorter than 0.4 s, and excellent EFC stability longer than 9000 s. Furthermore, by introducing viologen into electrolyte as a counter EC layer for charge balance, the resulting EFC device exhibits notable improvement in reducing oxidation potential (from 2.30 V to 1.55 V) and switching recovery time (from 78 to 38 s) with enhanced fluorescent contrast ratio during pulse on/off multi-cyclic scanning. These results demonstrate that incorporation of the EC and PL-active CN-PTPA is a facile and feasible approach to prepare highly efficient EFC devices.