A facile environmentally friendly hydrometallurgical approach to recover copper as nanoparticles from electronic waste (e-waste) has been presented. Selective leaching of copper from powdered old computers waste printed circuit boards (WPCBs) was executed in ammoniacal/ammonium salt solutions at room temperature. The effect of parameters controlling copper recovery has given due consideration. Copper nanoparticles were prepared from leachant solutions by reduction using L-ascorbic acid reductant and (CTAB) as a modifier at room temperature. Characterization tests for the produced copper nanoparticles were performed to confirm its structure. XRD analysis manifested the pure crystallinity phase of copper nanoparticles and TEM images revealed its spherical shape with particle size in the range of 5–32 nm. It is considered that the studied process is merely efficacious and environmentally sustainable for preparing copper nanoparticles from WPCBs with the intention of recycling e-waste to gain a higher valued product.