Intrinsic electric fields in AlxGa1-xN/AlyGa1-yN quantum wells embedded into p-i-n structures are studied using photoluminescence experiments. Spectral shifts induced by external bias and screening by photoexcited carriers allow evaluating the intrinsic fields caused by piezoelectric and spontaneous polarizations. In quantum wells with low Al content, the field is about 1 MV/cm, which is in agreement with theoretical estimations. For high Al molar fractions (35% well, 50% barrier), the extracted intrinsic field is lower and, most importantly, has the opposite sign to that predicted by the theory.