The epitaxial layers of InGaN/GaN MQWs structure were grown on both planar and vicinal sapphire substrates by metal organic chemical vapor deposition. By comparing the epitaxial layers grown on planar substrate, the sample grown on 4° misoriented from c-plane toward < 10 1 ̄ 0 > m-plane substrate exhibited many variations both on surface morphology and optical properties according to the scanning electronic microscopy and cathodoluminescence (CL) spectroscopy results. Many huge steps were observed in the misoriented sample and a large amount of V-shape defects located around the boundary of the steps. Atoms force microscopy images show that the steps were inclined and deep grooves were formed at the boundary of the adjacent steps. Phase separation was observed in the CL spectra. CL mapping results also indicated that the deep grooves could effectively influence the localization of Indium atoms and form an In-rich region.