High‐quality epitaxy consisting of Al_1−xGa_xN/Al_1−yGayN multiple quantum wells (MQWs) with sharp interfaces and emitting at ≈280 nm is successfully grown on sapphire with a misorientation angle as large as 4°. Wavy MQWs are observed due to step bunching formed at the step edges. A thicker QW width accompanied by a greater accumulation of gallium near the macrostep edge than that on the flat‐terrace is observed on 4° misoriented sapphire, leading to the generation of potential minima with respect to their neighboring QWs. Consequently, a significantly enhanced photoluminescence intensity (at least ten times higher), improved internal quantum efficiency (six times higher at low excitation laser power), and a much longer carrier lifetime are achieved. Importantly, the wafer‐level output‐power of the ultraviolet light emitting diodes on 4° misoriented substrate is nearly increased by 2–3 times. This gain is …