We present the studies on static and transient optical characteristics of electrospun poly[2-methoxy-5-(2(')-ethylhexyloxy)-1,4- phenylenevinylene]/poly(vinyl pyrrolidone) (MEH-PPV/PVP) nanofibers. [6,6]-phenyl-C61 butyric acid methyl ester is mixed into the polymer matrix, working as quenchers to optical excitons. Comparing with the spin-coated films, the nanofibers exhibit enhanced exciton migration in speed and amplitude. The results are explained together with photoluminescent spectra blueshifting and longer exciton lifetime. Reduced aggregation and long-range order simultaneously induced by electric field are regarded as the mechanism for the phenomena.