The oxide scales formed on Ni-18W(at.%) coating that was electrodeposited on steel were investigated using XRD, SEM and TEM. The oxide scales consisted mainly of an outer NiO layer, and an inner thick ($NiWO_4$+NiO) mixed layer. The unoxidized coating below the oxide scale was rich in Ni and depleted in W, owing to the consumption of Wand the resultant Ni enrichment. The oxidation resistance of Ni-18W coating was poorer than that of the TiN coating, due to the formation of nonprotective NiWO$_4$. During oxidation, Ni and the substrate element of Fe diffused outward, while oxygen inward, according to the concentration gradients.