The authors report on the direct integration of high-dielectric constant (high-k) Ta2O5 films on p-type single crystal diamond for high-power electronic devices. Crystallized hexagonal phase δ-Ta2O5 film is achieved on diamond by annealing the amorphous Ta2O5 film deposited by a sputter-deposition technique. The electrical properties of the Ta2O5 thin films are investigated by fabricating metal-insulator-semiconductor (MIS) diodes. The leakage current of the MIS diode is as low as 10−8 A/cm2 for the as-deposited amorphous Ta2O5 film and 10−2 A/cm2 for the crystallized film, which is 108 and 102 times lower than that of the Schottky diode at a forward bias of −3 V, respectively. The dielectric constant of the amorphous Ta2O5 films is measured to be 16 and increases to 29 after annealing at 800 °C. Different current leakage mechanisms and charge trapping behaviors are proposed for the amorphous and crystallized Ta2O5 thin films.