In this article, the tribocorrosion behaviors of NiCrMo-625 alloy sliding against an Al₂O₃ pin using a pin-on-disk tribometer have been carried out to assess the effect of electrochemical state on the corrosion–wear properties of the alloy in artificial seawater. The results shows that a cathodic shift in the open circuit potential of NiCrMo-625 alloy during tribocorrosion is confirmed and a marginal increase in corrosion current can be found under tribocorrosion compared to static corrosion. Total material loss of NiCrMo-625 alloy during tribocorrosion obviously increases with an increase in applied potential, indicating the synergistic effect between wear and corrosion. Although the corrosion rate of the alloy is significantly increased by sliding, the ratio of wear-induced corrosion to the total wear loss is not very large. The proportion of wear-induced corrosion and corrosion-induced wear to the total material loss increases obviously with an increase in potential.