We report on the growth and characterization of InGaN/GaN MQWs on two different types of sapphire substrates and GaN substrates. The InGaN/GaN MQWs are grown by using metalorganic chemical vapor deposition. Our analysis of the satellite peaks in the HRXRD patterns shows, GaN substrates InGaN/GaN MQW compared to sapphire substrates InGaN/GaN MQW, more compressive strain on GaN substrates than on sapphire substrates. However, results of optical investigation of InGaN/GaN MQWs grown on GaN substrates and on sapphire substrates, which have lower Stokes-like shift of PL to GaN substrates compared to sapphire substrates, are shown to the potential fluctuation and the quantum-confined Stark effect induced by the built-in internal field due to spontaneous and straininduced piezoelectric polarizations. The InGaN/GaN MQWs are shown to quantify the Stokes-like shift as a function of x.