Ultrafine poly [2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene-vinylene] (MEH-PPV)/poly(vinyl pyrrolidone) (PVP) composite fibers with the average diameters ranging from 43 nm to 1.7 mu m were prepared by electrospinning of blended polymer solutions in mixed solvent of chlorobenzene and methanol. The average diameter of the as-spun fibers was found to decrease into nanometer scale with decreasing the PVP concentration and/or addition of a volatile organic salt, pyridinium formate (PF). PVP was easily removed from MEH-PPV/PVP fibers by the Soxhlet extraction, and after the removal, pure MEH-PPV fibers were obtained as a ribbon-like structure aligned with wrinkled surface in fiber direction. Comparison with the cast film, as-spun fibers showed relatively higher crystallinity, higher conjugation length, and there was a remarkable blue shift of photoluminescence (PL) peak.