TiO 2 nanoparticles were introduced into the soluble sulfonium precursor of PPV (Poly(p-phenylene vinylene)) during the synthesis procedure of precursor. Later, PPV–TiO 2 nanofibers were prepared by electrospinning of precursor–TiO 2 solution, followed by thermal conversion. The fluorescence microscopy images showed that the resulting nanofibers exhibited outstanding emission properties. No significant differences were observed in photoluminescence spectra of PPV–TiO 2 and PPV fibers. A single oriented PPV–TiO 2 nanofiber can be obtained on the substrate by a modified electrospinning method, which is favorable for some practical applications such as electrical and optical nanodevices.