In this study we present the results of electroless deposition of silver (Ag) and silver tungsten [Ag(W)] layers on Si, intended for application in microelectronics and microelectromechanical systems (MEMS) technology. Silver has excellent resistivity but its thin-film properties and its vulnerability to corrosion may cause a problem. In this work we present a novel Ag(W) type of layer that has improved thin-film properties, such as resistivity and surface roughness, and can serve as both barrier layer and capping layer for corrosion protection of the Ag thin films. The thin-film composition was studied as a function of the deposition parameters. We found the presence of tungsten, up to 3.1 atom %, and oxygen, up to 8 atom %, in addition to the silver atoms. We also studied the thin-film morphology using atomic force microscopy and scanning tunneling microscopy imaging of the surface after each process step. Finally, we discuss the possible mechanisms for the deposition of Ag(W).