In this study, the performance of AlN (0001)/Hf (0001) interface, such as occupation characteristics and combined energy, were studied by using the first principles calculation package. In the AlN/Hf interface, the Al- and N-terminated interfaces have three stacking sites each (outermost top site, sub-outer top site, and hexagonal close-packed hollow site), comprising six different models. The most adhesion work occupies the N-terminal interface of the hcp-hollow site, and the interface energy was also the smallest and most stable, as well as a lower fracture work than the AlN/Ti interface. Moreover, the differential charge density were calculated, the partial density of states were plotted, and the bonding properties were discussed. Compared with other interfaces, the N-terminated interface with the hcp-hollow site exhibited more covalent characteristics; on the Al-terminated interface with the sub-outer top site, the Hf-Al metallic bond was formed. The most stable atomic occupation type in AlN/Hf interface is the hcp-hollow site of N atomic terminal.