In this paper, the 10 nm p-NiO thin film is prepared by thermal oxidation of Ni on the β-Ga2O3 to form NiO/β-Ga2O3 p-n heterojunction diodes (HJDs). The NiO/β-Ga2O3 HJDs exhibit excellent electrostatic properties, with a high breakdown voltage of 465 V, a specific on-resistance (Ron,sp) of 3.39 mΩ·cm2, a turn-on voltage (Von) of 1.85 V, yielding a static Baliga’s figure of merit (FOM) of 256 MW/cm2. Also the HJDs have low turn-on voltage, which reduces conduction loss dramatically, and a rectification ratio of up to 108. Meanwhile, the HJDs reverse leakage current is essentially unaffected at temperatures below 170 ℃, and its leakage level may be controlled below 10-10 A. It indicates that p-NiO/β-Ga2O3 HJDs with good thermal stability and high-temperature operating ability turn to be an effective route for high-performance β-Ga2O3 power devices.