The luminescent properties of AlGaN epitaxial layers with AlN mole fractions up to 30% and various types of AlGaN/GaN-based heterostructures have been studied. The structures were grown on 6H-SiC substrates by MOCVD. The structures' cathodoluminescence and electroluminescence were measured. A “blue” shift of the edge luminescent peak position for AlGaN alloys was measured to be a non-linear function on the AlN mole fraction. For p-AlGaN/n-GaN double heterostructures (DH), the edge peak position was detected at 365 nm (300K). For a p-Al0.05Ga0.95N/n-Al0.03Ga0.97N heterostructure, the electroluminescent edge peak was observed at 355 nm (300K). The effects of temperature and forward current on the edge electroluminescence of theAlGaN/GaN DH's were investigated.