In the present study, Co-W nano-structured alloy coatings are produced on low-carbon steel substrate by means of pulse electrodeposition from a citrate-based bath under different average current densities and duty cycles. The results indicate that the coating deposited under 60% of duty cycle and 1 A/dm2 of average current density exhibit optimum pulse plating conditions with 44.38 wt.% W, 37 nm grain size, and 758 HV microhardness. The effect of heat treatment temperature on microstructure, composition, corrosion behavior, and morphology of amorphous deposited Co-W alloy with 44 wt.% W was investigated. The microhardness of the coating increased to 1052 HV after heat treatment at 600 °C, which is due to the formation of Co3W and CoWO4 phases in the deposit. Furthermore, the coatings heat-treated at 600 °C had lower friction coefficients and better wear resistance under various loads than before heating.