Polarization effects have been studied in GaN/AlGaN multiple quantum wells (MQWs) with different c-axis orientation by means of excitation-dependent photoluminescence (PL) analysis. Quantum structures were grown on [0001]-oriented sapphire substrates (C plane) and single-crystalline [11̄00]-oriented freestanding GaN (M plane) using the metalorganic chemical vapor deposition technique. Strong PL spectrum line blueshifts (up to 140 meV) which are correlated with the excitation intensity have been obtained for C-plane MQWs, whereas no shift has been observed for M-plane MQWs. Theoretical calculations and comparison with the PL data confirm that the built-in electric field for C-plane structures is much stronger than the field present for M-plane MQWs. In the former case, the excitation-induced blueshift of the PL line is due to the screening of the built-in electric field by photoinjected carriers, which is consistent with the field strength of 1.23 MV/cm in the absence of excitation.