Copper (Cu) containing composite nanofibres was prepared by electrospinning and the high-pressure hydrogenation method. Copper nitrate has been mixed in the polymeric precursor solution before electrospinning. The nanofibres were characterised by using scanning electron microscopy, UV-vis spectroscopy, energy dispersive spectroscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The observations revealed the embedding of polyacrylonitrile (PAN) nanofibres with Cu nanoparticles. It was also found that Cu nanoparticles were significantly protected by PAN nanofibres. The combination of electrospinning and the high-pressure hydrogenation method will provide a new approach to producing the functional materials with various applications.