The three-dimensional palladium networks and palladium-silver bimetallic alloy networks were synthesized at room temperature in large scale using a rapid and simple strategy. The results revealed that the morphology of the networks does not affected by the composition. We demonstrated that the as-prepared unsupported networks exhibited excellent electrochemical activity and stability toward ethanol oxidation reaction in alkaline media due to the formation of palladium-silver alloy as well as the porous nanostructures. The results indicate that the well-defined three-dimensional palladium-silver bimetallic alloy networks are promising catalysts for fuel cells.