We report an efficient non-doped all-polymer polymer white-light-emitting diode (PWLED) with a fluorescent three-color, white single polymer as an emissive layer, an ethanol-soluble phosphonate-functionalized polyfluorene (PF-EP) as an electron-injection/electron-transport layer, and LiF/Al as a cathode, respectively. The all-polymer PWLED achieves a peak external quantum efficiency of 6.7%, a forward viewing luminous efficiency of 15.4 cd A(-1) and a power efficiency of 11.4 lm W-1, respectively, at a brightness of 347 cd m(-2) with Commission Internationale d'Eclairage coordinates of (0.37, 0.42) and color rendering index of 85, which is the best results among the non-doped PWLEDs. Moreover, this kind of PWLED not only shows excellent color stability, but also achieves high brightness at low voltages. The brightness reaches 1000, 10000, and 46830 cd m(-2) at voltages of 4.5, 5.4, and 7.5 V, respectively. The significant enhancement of white-single-polymer-based PWLEDs with PF-EP/LiF/Al to replace for the commonly used Ca/Al cathode is attributed to the more efficient electron injection at PF-EP/LiF/Al interfaces, and the coordinated protecting effect of PF-EP from diffusion of Al atoms into the emissive layer and exciton-quenching near cathode interfaces. The developed highly efficient non-doped all-polymer PWLEDs are well suitable for solution-processing technology and provide a huge potential of low-cost large-area manufacturing for PWLEDs.