Polarization-reversed electron-blocking structure, which had negative polarization charges localized at the interface between the last quantum barrier (LQB) and electron-blocking layer (EBL), was demonstrated to remarkably improve the light-emitting efficiency of GaN-based blue light-emitting diodes (LEDs) numerically and experimentally. The improvement was attributed to the enhanced electron-blocking effectiveness by the elevated conduction band nearby the LQB/EBL interface. Nevertheless, the efficiency droop was not mitigated because the decrease of electron-leakage was accompanied by the increase of Auger recombination.