The comparative study of photoluminescence (PL) dynamics of wurtzite-type GaN/AlGaN multiple quantum wells (MQWs) fabricated using low-pressure metalorganic chemical vapor deposition technique over GaN coated -sapphire (C-plane) and single crystalline -oriented freestanding GaN (M-plane) substrates is presented. The MQWs on C-plane sapphire at low excitation exhibited much lower (∼30 times) PL intensity in comparison with M-plane samples. The C-plane MQWs showed a strong excitation intensity-induced PL spectrum line blueshift (up to 140 meV). Meanwhile identical MQW structures on M-plane substrates demonstrated no PL peak shifts indicating an absence of polarization fields. At higher excitation (>50 kW/cm2) the PL intensity and spectra peak positions for both the C- and the M-plane MQWs become nearly the same and do not differ with subsequent increase of pumping. Theoretical analysis and comparison with PL experimental data revealed strong (up to ∼1.2–1.3 MV/cm) built-in electrostatic fields in the C-plane structures whereas M-plane structures are almost non-polar.