In this paper, an n-i-p-type GaN barrier for the final quantum well, which is closest to the p-type GaN cap layer, is proposed for nitride light-emitting diodes (LEDs) to enhance the confinement of electrons and to improve the efficiency of hole injection. The performances of GaN-based LEDs with a traditional GaN barrier and with our proposed n-i-p GaN barrier were simulated and analyzed in detail. It was observed that, with our newly designed n-i-p GaN barrier, the performances of the LEDs were improved, including a higher light output power, a lower threshold voltage, and a stronger electroluminescence emission intensity. The light output power can be remarkably boosted by 105% at an injection current density of 100 A/cm2 in comparison with a traditional LED. These improvements originated from the proposed n-i-p GaN barrier, which induces a strong reverse electrostatic field in the n-i-p GaN barrier. This field not only enhances the confinement of electrons but also improves the efficiency of hole injection.