Nanofibers consisting of the bulk heterojunction organic photovoltaic (BHJOPV) electron donorelectron acceptor pair poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) are produced through a coaxial electrospinning process. While P3HT:PCBM blends are not directly electrospinnable, P3HT:PCBM-containing fibers are produced in a coaxial fashion by utilizing polycaprolactone (PCL) as an electrospinnable sheath material. Pure P3HT:PCBM fibers are easily obtained after electrospinning by selectively removing the PCL sheath with cyclopentanone (average diameter 120 +/- 30 nm). These fibers are then incorporated into the active layer of a BHJOPV device, which results in improved short-circuit current densities, fill factors, and power-conversion efficiencies (PCE) as compared to thin-film devices of identical chemical composition. The best-performing fiber-based devices exhibit a PCE of 4.0%, while the best thin-film devices have a PCE of 3.2%. This increase in device performance is attributed to the increased in-plane alignment of P3HT polymer chains on the nanoscale, caused by the electrospun fibers, which leads to increased optical absorption and subsequent exciton generation. This methodology for improving device performance of BHJOPVs could also be implemented for other electron donorelectron acceptor systems, as nanofiber formation is largely independent of the PV material.