The model system of the InGaN/GaN quantum wells (QWs), based on the first principles calculation, was chosen to understand the underlying mechanism of interfacial polarization and its synergic effect with the built-in electric field (B ef ) at the p−n junction in solar cells (SLs). The polarized electric field (P ef ) was generated due to the redistribution of electrons and holes at the interface; moreover, the P ef of InGaN/GaN heterostructure on the semipolar (01-11) GaN surface was consistent with that of on the N-polar (000-1) surface, which is on the lines of the B ef and favors the electron−hole separation efficiency in SLs. Furthermore, the growth of high-quality InGaN/GaN QWs on the semipolar (01-11) GaN surface was achieved. Such an atomic-scale investigation provides a fundamental understanding of the polarization chargeinduced P ef and its interaction coupling with B ef at the p−n junction, which could be generalized to polar material-based SLs.