Electrospinning method to fabricate copper nanofibers spread on a substrate as transparent conductive films was studied. The processing steps are electrospinning of Cu solutions (Cu source materials + liquefaction polymer solu- tions) to form nanofibers, annealing in air ambient to remove polymer material and oxidize Cu, and annealing in hydrogen ambient to change copper oxide nanofibers to copper nanofibers. Two kinds of diluent and liquefaction solutions of PVA and PVB were tested. PVA showed a reaction with Cu acetate with mixing. This led to a high annealing temperature of 500∘C for removal of PVA from the mixture. The high temperature oxidation possibly led to a high crystallinity CuO, which in turn increased the reduction temperature required. It was 500∘C in hydrogen ambient or Cu nanofiber network formation. The high reduction temperature was the main reason for the Cu nanofibers melting and consequent disconnection. In the meantime, Cu nitrate trihydrate mixing with PVB required lower oxidation and reduction temperatures of 450∘C and 300∘C, respectively. The fabricated Cu nanofiber network led to a percolation condition, and a relatively simple economic procedure was developed. However, the heat treatment temperatures need to be further lowered for application to flexible polymer substrates.