The optical performance and relevant physical properties of near-ultraviolet (NUV) GaN-based light-emitting diodes (LEDs) are investigated. Specifically, the influence of traditional AlGaN bulk electron blocking layer (EBL) and AlGaN/GaN superlattice (SL) EBL with various thicknesses of AlGaN layers on NUV LEDs is explored. It is indicated from the band diagrams, electrostatic field profile, electron reflecting and hole transmitting spectra, and carrier concentrations profile that the use of a thin AlGaN layer of AlGaN/GaN SL EBL is beneficial to the electron confinement and hole injection in the active region, which results in the high internal quantum efficiency and low efficiency droop at high injection current. Moreover, the experimental results show that replacing the traditional AlGaN bulk EBL with the AlGaN/GaN SL EBL can markedly improve the optical performance. When compared with the NUV LED with traditional AlGaN bulk EBL, the output power of the NUV LED with the proposed AlGaN/GaN SL EBL increases from 13.5 to 48.7 mW at 100 mA.