Cu nanofiber networks can be a good alternative of the Ag nanowire of high electrical conductivity while having the advantage of low price. An electrospinning method was developed to fabricate copper nanofiber network for use as a transparent conductive film on glass substrate. The effects of liquid diluents for electrospinning processability were examined in relation to the subsequent Cu nanofiber formation processes. Electrospinning solutions of copper acetate/polyvinyl alcohol (PVA) and copper nitrate trihydrate/polyvinyl butyral (PVB) were investigated. The polymer mixing solutions influenced the subsequent annealing temperatures for removal of the polymers and reduction of the formed CuO nanofibers to Cu metal nanofibers. The morphology and structures of the formed nanofiber networks were examined by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction, and so forth. The mixture with PVB provided lower annealing temperatures suitable for application to flexible substrates.