Bimetallic core-shell nanostructures have attracted increasing attention due to their low material costs along with enhanced chemico-physical properties in comparison with their monometallic counterparts. Here, a novel gold. decorated nanoporous copper (Au@NPC) core-shell composite fabricated by a facile in situ hydrometallurgy approach is reported. Thin gold shells with a controllable thickness are homogeneously deposited onto the internal surfaces of 3D nanoporous copper via a spontaneous displacement reaction while nanoporous copper is utilized as a reduction agent as well as 3D template and substrate. The resulting inexpensive core-shell nanostructure exhibits significant electrocatalytic activity for the oxidation of methanol and high non-enzymatic sensitivity in detecting glucose.