High‐quality epitaxy consisting of Al1−xGaxN/Al1−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 attributed to the introduction of compositional inhomogeneities in AlGaN alloys induced by gallium accumulation at the step‐bunched region thus forming a lateral potential well for carrier localization. The experimental results are further confirmed by a numerical modeling in which a 3D carrier confinement mechanism is proposed. Herein, the compositional modulation in active region arising from the substrate misorientation provides a promising approach in the pursuit of high‐efficient ultraviolet emitters.