In this study, a block-on-ring wear tester was employed to investigate the tribocorrosion behavior of electrodeposited Ni-W coatings. Passivation of the Ni-W alloy was observed according to the potentiodynamic polarization curve obtained in a 5 wt% NaCl solution. The result showed that with an increase in the applied overpotential, both the wear rate and the surface W-content of the coating increased. On the other hand, the accompanying coefficient of friction decreased with the increasing overpotential. The FESEM micrograph showed that small pits and cracks appeared on the tested specimen. This micro-cracking phenomenon was also observed in the corroded zone of the Ni-W coating by using TEM microscopy. The XPS analysis confirmed the formation of a passivated film on the corroded surface.