Poly [2-methoxy-5-(2'-ethyl-hexyloxy)- 1,4-phenylene vinylene] (MEH-PPV) is an excellent conjugated polymer and broadly used in the polymer photoelectron devices, but difficult to be electronspun directly. In the present study, the core-shell structured nanofibers were fabricated by coaxial electrospinning MEH-PPV (shell) in chlorobenzene and PVP (core) in 1,2-dichloroethane. MEH-PPV was soluble in the above two solvents, which prevented the precipitation of MEH-PPV and enhanced the adhering action between the two polymers in coaxial electrospinning process. We anticipate that these uniform core/shell PVP/MEH-PPV nanofibers with highly fluorescent property will have potential applications in the fabrication of polymer nano-photoelectron devices. (c) 2007 Elsevier Ltd. All rights reserved.