Electrospinning is a simple technique to form high surface area membranes using large static electric potentials. An application, taking advantage of such a high surface area, is a dye-sensitized photovoltaic cell, wherein a chromophore molecule absorbs light before being oxidized to generate a photocurrent. We report functioning photovoltaic cells made from polyacrylonitrile fibers infused with the azo-dye, Congo Red in a liquid-junction cell assembly. Cell performance of the electrospun cells compared favorably to cells made by spin-coating thin films of polyacrylonitrile and Congo Red. Also reported are the effects of adding nanoparticles of titanium dioxide to the cells. Finally, the maximum amount of dye that can be incorporated into a fiber is presented.