Thin film of silver (Ag) and its composition with tungsten (Ag-W) has been deposited by the electroless method on Pd activated (100) silicon, silicon dioxide, as well as on silver and cobalt seed-layers. The specific resistivity of Ag-W films were as low as 2 μΩ · cm and their reflectivity exceeds 90%. The added tungsten to the silver in the thin film improved significantly its corrosion stability and increased its hardness. The corresponding nano/atomic-level studies indicated on a structure similar to the silicon substrate. The role of tungsten in the silver matrix is in the form of WO3- salt, hence to produce the second phase particle (SPP) effect. The electroless deposited thick Ag-W layer has a spiral structure that is typical for the electrochemical mechanism of the film grouth.