GaInN/GaN heterostructures and quantum wells have been grown by low pressure metalorganic vapor phase epitaxy on sapphire using an AIN nucleation layer. We found a significant In incorporation only for growth temperatures of 700°C, although still very high In/Ga ratios in the gas phase had to be adjusted. The In content could be increased by reducing the H2/N2 flow ratio in the main carrier gas. GaInN layers typically show two lines in low temperature photoluminescence which are identified as excitonic-like (high energy peak) and impurity-related-like (low energy) by time-resolved spectroscopy. Quantum wells with a thickness between 8 and 0.5 nm showed only one emission line. The peak of the thinnest wells shows excitonic-like behaviour, whereas we found a smooth transition to an impurity-related-like type with increasing thickness. By scanning transmission electron microscopy studies we found indications for composition fluctuations in these thicker quantum wells which may cause localization effects for the excitons and thus be responsible for the observed optical spectra.