Ag-W alloy contact is one kind of important electrical contact materials, and the separation and recycling of sliver and tungsten from waste Ag-W alloy contact has attracted more and more attention for the resource value and secondary pollution during the recycling process. A novel process about the separation and recycling of sliver and tungsten from waste Ag-W alloy contact has been proposed, which includes 4 steps of first leaching silver, roasting, secondary leaching silver and ammonia leaching. The result shows that the recovery rate of Ag and W is higher than 99%, and 0.3-0.6 μm superfine silver powders and pure WO3 powders can be obtained during the recycling process.