Composite nanostructured foams consisting of a metallic shell deposited on a polymeric core were formed by plating copper via electroless deposition on electrospun polycaprolactone (PCL) fiber mats. The final structure consisted of 1000-nm scale PCL fibers coated with 100s of nm of copper, leading to final core-shell thicknesses on the order of 1000-3000 nm. The resulting open cell, core-shell foams had relative densities between 4 and 15 %. By controlling the composition of the adjuncts in the plating bath, particularly the composition of formaldehyde, the relative thickness of copper coating as the fiber diameter could be controlled. As-spun PCL mats had a nominal compressive modulus on the order of 0.1 MPa; adding a uniform metallic shell increased the modulus up to 2 MPa for sub-10 % relative density foams. A computational materials science analysis using density functional theory was used to explore the effects pretreatment with Pd may have on the density of nuclei formed during electroless plating.