ZnO and Ce-doped ZnO Nanofibers on (111) Pt/SiO2/Si substrates were produced using an electrospinning technique. The as-prepared composite fibres were subjected to high-temperature calcination to produce inorganic fibers. After calcining at a temperature of 500 °C, the average diameter of the ZnO and Ce-doped ZnO nanofibers were determined to be 170 nm and 225 nm, respectively. The average grain size of the ZnO and Ce-doped ZnO nanofibers were about 50 nm and 57 nm, respectively. The microstructure, chemical bonding state and photoluminescence of the produced ZnO and Ce-doped ZnO nanofibers were investigated. The Ce-doped ZnO nanofiber can be assigned to the presence of Ce ions on substitutional sites of Zn ions and the Ce3+ state from X-ray photoelectron spectra. Compared with PL spectra of ZnO nanofibers, the peak position of the UV emission of the Ce-doped ZnO nanofibers is sharply suppressed while the green emission band is highly enhanced.