Owing to poor hole-injection efficiency, conventional AlGaN-based deep-ultraviolet (DUV) light-emitting diodes (LEDs) generally suffer from a seriously inhomogeneous carrier distribution in the quantum well region. This leads to uneven radiative recombination rates, seriously affecting the luminous efficiency. In this paper, however, we propose an asymmetric quantum well (AQW) near the interface between the last quantum barrier and the electron blocking layer to fully utilize the inhomogeneous distribution characteristics. The optoelectronic performances of conventional and a proposed DUV-LED with an AQW have been numerically simulated and analyzed. The results reveal that electrons and holes tend to gather and recombine in the AQW region. This significantly enhances the internal quantum efficiency and the light output power with an improvement of about 120%, although it increases the peak emission wavelength red-shift. The peak emission wavelength of the AQW can be adjusted to the wavelength of the original structure while keeping a high optical efficiency by simply increasing the Al composition.