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Room temperature contactless electroreflectance (CER) has been applied to study optical transitions and the distribution of the built-in electric field in AlGaN/GaN heterostructures grown on c-, a-, m-, and (20.1)-plane GaN substrates obtained by the ammonothermal method. It has been clearly shown that polarization effects in the AlGaN/GaN heterostructures grown on the c-plane lead to a strong built-in electric field in the AlGaN layer. The aforementioned field was determined to be ∼0.43 MV/cm from the period of Franz–Keldysh oscillations (FKOs). In addition, polarization effects lead to the formation of a two dimensional electron gas at the AlGaN/GaN interface, which screens the band bending modulation in the GaN buffer layer, and, therefore, GaN-related excitonic transitions are not observed for this heterostructure. Such features/effects are also not observed in the AlGaN/GaN heterostructures grown on nonpolar and semipolar GaN substrates because any strong polarization effects are not expected in this case. For these heterostructures, very strong and sharp GaN excitonic resonances are clearly visible in CER spectra. The resonances are very similar to the excitonic transitions observed for the GaN epilayers deposited on nonpolar and semipolar substrates. Moreover, there is a very weak AlGaN-resonance without FKO for nonpolar and semipolar heterostructures instead of the strong AlGaN-related FKO, which is typical of polar AlGaN/GaN heterostructures.