The ultra-wide bandgap semiconductor diamond represents a promising potential for advancement and innovation in the field of electronic device development. Utilizing first-principles calculations, a thorough investigation has been performed on the structural and electronic characteristics of MOx/diamond (MOx = HfO2, ZrO2, TiO2, Al2O3, Sc2O3, Y2O3) heterostructures. The concentration of charge transfer at the high-κ oxide/diamond interfaces leads to obvious interface polarity localization characteristics. The studied MOx/diamond heterojunctions feature insulating interfaces without any gap states. The MOx/diamond supercells exhibit the ability to effectively confine holes on the diamond surface owing to the large band offsets (>1 eV), showing typical electronic properties of “type II” staggered energy band configurations. These findings demonstrate that the high-κ oxide MOx/diamond can serve as highly promising diamond gate dielectrics, and provide theoretical insights into the interfacial engineering of diamond MOS devices.