Metal/AlN/n‐type 6H–SiC(0001) heterostructures have been prepared by growing wurtzite AlN layers on vicinal 6H–SiC(0001) using gas‐source molecular beam epitaxy. High‐resolution transmission electron microscopy results show that the interface between the AlN layer and the Si‐terminated 6H–SiC substrate is microstructurally abrupt, but contains defects originating at step sites on the 6H–SiC surface. The interface is found to have a low density of trapped charges of 1×1011 cm−2 at room temperature without any postgrowth treatment. This value is comparable to those reported for thermally grown and deposited oxides on n‐type 6H–SiC(0001), and indicates the formation of a high quality interface.