Molecular beam deposited zirconium dioxide (ZrO2) was assessed as high-κ gate dielectric for future GaN based devices. To compare and study electrical and structural properties, thin ZrO2 films were deposited on three different substrates, n++-c-plane GaN, p-(100) Si, and TiN. The films were fabricated by electron beam evaporation from a single stoichiometric ZrO2 target. A substrate-independent phase transition from amorphous ZrO2 to the tetragonal/cubic phase was identified by gracing incidence x-ray diffractometry. Finally, monoclinic ZrO2 emerged with increasing film thickness. As found by x-ray photoelectron spectroscopy, ZrO2 formed an abrupt interface to both GaN and TiN without intermixture. Dielectric constants in the range of 14–25 were extracted from capacitance versus voltage measurements for as-deposited ZrO2 films. The leakage currents of ZrO2 on GaN resembled their counterparts on Si as well as on TiN.