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Templates consisting of in-plane alternately arranged relaxed InGaN and GaN were obtained by (11–22) facet growth and mass transport via metal-organic vapor phase epitaxy. InGaN/GaN multi-quantum wells (MQWs) were grown on the novel templates, and their optical and structural properties were investigated. From photoluminescence measurement, longer and shorter peak emission wavelengths were observed from the MQWs on the InGaN and GaN regions, respectively. The discrepancy of the peak emission wavelength for the MQWs on the alternately arranged relaxed InGaN and GaN was caused by the compositional-pulling effect, which contributed to the InN molar fraction and the thickness of the InGaN quantum well. The reduction of the quantum-confined Stark effect on the InGaN region of the template was confirmed by revealing the structural and optical properties of the MQWs.