In this paper, we report the effects of polyvinyl alcohol (PVA) and CdS quantum dots (QDs) on the photoluminescence (PL) properties of poly(phenylene vinylene) (PPV) nanofibers. The composite nanofibers were fabricated by coupling self-assembly and electrospinning method. A significant blue shift in both PL spectra and fluorescence images of PPV fibers was observed after doping of CdS QDs and PVA in succession. It was found that the changes in PL spectra of PPV originated from the chemical interactions between PPV and PVA, and the changes in the crystallization of PPV itself. A possible PL mechanism was proposed accordingly. (C) 2010 Published by Elsevier B.V.