Two practically fully relaxed AlN domains were identified by x-ray diffractometry for AlN grown on (100) diamond. The epitaxial orientation relationships (0001)[101¯0] AlNI‖(100)[011] diamond for the predominant AlN domain (type I) and (0001)[1¯21¯0] AlNII‖(100)[011] diamond for the second domain (type II) are obtained. Surface morphology measurements corroborate the good structural quality of the AlN film. In addition, the intrinsic built-in voltage of a n-AlN∕p-diamond diode was determined as 1.15V. By spectrally resolved photocurrent measurements, the ultraviolet electroluminescence emission was confirmed to originate at the heterojunction interface, and is most probably due to a defect center.