In this study, the superlubricity stability of hydrogenated diamond-like carbon (H-DLC) film in vacuum was investigated by varying the sliding velocity (30–700 mm/s). The relatively stable superlubricity state can be maintained for a long distance at low sliding velocity, whereas the superlubricity state quickly disappears and never recovers at high sliding velocity. Under superlubricity state, the transfer layer of H-DLC film was observed on the Al₂O₃ ball, which played a key role in obtaining ultra-low friction coefficient. Although the transfer layer can be generated at the beginning of the test, high-velocity sliding tends to accelerate the superlubricity failure and leads to the severe wear of H-DLC film. Analysis indicated that the main reason for superlubricity failure at high sliding velocity is not attributed to friction heat or the break of hydrogen passivation but to the absence of transfer layer on Al₂O₃ ball. The present study can enrich the understanding of superlubricity mechanism of H-DLC film.