Rectification abilities of tungsten carbide (WC) Schottky‐barrier diodes fabricated on p‐type diamond were confirmed up to 800 K. In this study, electrical properties were used to support the investigation of the WC/diamond interface reaction under elevated temperature. Before heating above 500 K, the interface was not thermally stable. The interface has been stabilized by mean of an annealing under vacuum in the 550–600 K range. This treatment has produced diodes exhibiting large rectification factors of 106 at 3 V, and low leakage currents of 10−12 amps at 100 V in the blocked state, when the operation temperature was below 600 K. However, rectification factors were gradually worsened, while the temperature was exceeding 600 K.