Copper-loaded carbon nanofibers are fabricated by thermally treating electrospun Cu(CH3COO)2/polyacrylonitrile nanofibers and utilized as an energy-storage material for rechargeable lithium–ion batteries. These composite nanofibers deliver more than 400mAg−1 reversible capacities at 50 and 100mAg−1 current densities and also maintain clear fibrous morphology and good structural integrity after 50 charge/discharge cycles. The relatively high capacity and good cycling performance of these composite nanofibers, stemmed from the integrated combination of metallic copper and disordered carbon as well as their unique textures and surface properties, make them a promising electrode candidate for next-generation lithium–ion batteries.