The process and properties of electroless plating Ni-W-B alloy have been studied. The results show that the deposits containing W and B are obtained, and the deposition rate of the bath is increased with increase of W content when a certain amount of sodium tungstate solution is added in the Ni-B bath. The Ni-W-B alloy is amorphous as deposition and its resistivity increases directly with the increase of W content in the coating, but decreases gradually with increasing the deposit thickness. XRD and SEM show that the distributions of W and B in the Ni-W-B alloy film are very uniform and dispersed without any segregation.