Poly(3-hexylthiophene) (P3HT) nanofibers were fabricated with an association of poly(vinyl pyrrolidone) (PVP) by electrospinning. A mixture of P3HT/PVP in a mixed solvent of chlorobenzene and methanol was electrospun to form composite fibers with 60 nm - 2 μm in diameter, followed by getting rid of PVP by selective extraction. After extraction, pure P3HT nanofibers were obtained as a spindle-like structure with wrinkled surface. The nanofibers obtained exhibit specific features of strong interchain contribution as investigated by UV-vis, fluorescence spectroscopic, X-ray diffraction (XRD), and photo-electron investigations. Bulk heterojunction P3HT:PCBM nanofibers with ∼200 nm in diameters were also successfully fabricated by using the same technique. The preliminary results from the study of P3HT:PCBM nanofiber-based photovoltaic cells with conversion efficiency over 0.2% could be achieved. © 2011 Materials Research Society.