A polycrystalline Cu foam with sub-micron ligament sizes was formed by creating a non-woven fabric via electrospinning with a homogeneous mixture of polyvinyl alcohol(PVA)-and copper acetate(Cu(Ac)2). Thermogravimetric measurement of the electrospun fabric of the precursor solution is reported. Oxidizing the precursor fabric at 773K formed an oxide nano-foam; subsequent heating at 573K with a reducing gas transformed the CuO nano-foam to Cu with a similar ligament and meso-scale pore size morphology. A cross-section prepared by focused ion beam lift-out shows the polycrystalline structure with multi-scale porosity. The mechanical property of the Cu nano-foam is measured by nano-indentation. The load-depth curves and deduced mechanical properties suggest that additional intra-ligament pores lead to unique structure-property relations in this non-conventional form of metal.