The temperature-dependent behavior of on/off ratio and reverse recovery time in vertical heterojunction p-NiO/β n-Ga2O/n+ Ga2O3 rectifiers was investigated over the temperature range of 25–300 °C. The device characteristics in forward bias showed evidence of multiple current transport mechanisms and were found to be dependent on the applied bias voltages and temperatures. The on–off ratio decreased from 3 × 106 at 25 °C to 2.5 × 104 at 300 °C for switching to 100 V reverse bias. For 200 μm diameter rectifiers, the reverse recovery time of ∼21 ns was independent of temperature, with the Irr monotonically increasing from 15.1 mA at 25 °C to 25.6 mA at 250 °C and dropping at 300 °C. The dI/dt increased from 4.2 to 4.6 A/μs over this temperature range. The turn-on voltage decreased from 2.9 V at 25 °C to 1.7 V at 300 °C. The temperature coefficient of breakdown voltage was negative and does not support the presence of avalanche breakdown in NiO/β-Ga2O3 rectifiers. The energy loss during switching from 100 V was in the range 23–31 μJ over the temperature range investigated.