We report a novel multilayer electro-chemical polymerization method and the first color-stable polymer-based multilayer white-emissive device, which exhibited CIE coordinates of (0.35, 0.35), a CRI of 93 and extremely stable white-light emission over a wide range of driving voltages of 8 to 20 V. The multilayer electro-chemical polymerization method affords more opportunities to develop multilayer polymer heterostructures in organic solid-state devices.