Cerium (III) nitrate/poly(vinylpyrrolidone) (Ce(NO3)(3)/PVP) composite fibres have been prepared by electrospinning. After calcining the composite fibres in air at 500 degrees C, CeO2 nanowires were obtained. The characterizations of the as-spun composite fibres and resultant nanowires have been carried out by a scanning electron microscope (SEM), an infrared spectrometer, an x-ray diffractometer and a fluorescence spectrophotometer. Interestingly, some unusual ribbon-like or twin fibres were observed besides the common fibres with circular or elliptic cross sections. We developed a fibre-division model resulting from Coulomb repulsion and solvent vaporization to interpret the formation of the ribbons or twin fibres, which has been confirmed by the SEM studies. Our results also indicate that the formation of the ribbons or twin fibres is less dependent on operation voltage and work distance.