Electrospinning is a simple and effect technology which can produce continuous nanofibers. We get aligned electrospun nanofibers successfully by using parallel electrodes. We report our studies on transient fluorescence of aligned electrospun fibers. The fibers are excited and their fluorescences are observed both at axial and radial polarization. Steady-state PL spectra shows radial emission blue-shift more than axial!emission, due to weakened aggregation of molecular chains in radial direction. At all emission wavelength, radial emission excitons migrate faster than axial emission excitons.