Dye-sensitized solar cells exhibit promising efficiencies relative to the low cost of materials and fabrication, and improvements in efficiency can be achieved through the introduction of controllable nanostructures which enhance light-harvesting and charge transport characteristics. Electrospun TiO 2 nanofiber networks present a suitable structure for both light scattering and charge transport, though they exhibit insufficient mechanical properties and surface area compared to conventional nanoparticle networks. In this work TiO2 nanoparticle-nanofiber composite networks were generated, and the formation of unique fiber-pore structures was characterized and elucidated. The results demonstrated that enhancement in light-scattering by formation of the fiber-pore structures increased the efficiency of NP-NF composite DSSCs by 10% relative to conventional electrodes. The excellent control of the structural dimensions encourages promising application of these composites for DSSCs and other areas of electronics and optoelectronics.