A novel electrospun polymer-fiber solar cell was synthesized by electrospinning a 1 : 2.5 weight% ratio mixture of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) resulting in bulk heterojunctions. Electrospinning is introduced as a technique that may increase polymer solar cell efficiency, and a list of advantages of the technique applied to solar cells is discussed. The device achieved a power conversion efficiency of %. The absorption and photoluminescence of MEH-PPV nanofibers are compared to thin films of the same material. Electrospun nanofibers are discussed as a favorable structure for application in polymer solar cells.