Poly(3-hexylthiophene) nanowires, microns in length and nanometers in diameter, are stably suspended in solution, and crystallize by adjusting solvent strength. Cocrystalization of P3HT with P3HT-covered CdSe nanorods gave hybrid nanostructures in which the p-type P3HT fibrils were flanked by the n-type CdSe nanorods. The close proximity and arrangement of the two materials provides direct, continuous pathways suitable for charge transport in photovoltaic devices.