We report the results from detailed optical spectroscopy from MOCVD grown GaN/AlGaN multiple quantum wells (MQWs), as opposed to most previous studies where MBE was employed by means of photoluminescence (PL) technique. In this paper we will present theoretical and experimental results demonstrating how polarization induced electric fields and bound interface charges in GaN/AlGaN MQWs affect the emission peak energy, PL line shape, as well as the emission line width. Theoretically estimated fields in this work are consistent with experimental data. Transition energy of the heavy hole and electron ground state Ee-hh in GaN/AlGaN MQWs were calculated and it is found that it stays in good agreement with the experimental data.