In this study, we developed a novel nanostructured polymer nanofiber/TiO2 nanoparticle composite photoelectrode with high bendability by a spray-assisted electrospinning method. The composite film is used as the photoelectrode in plastic dye-sensitized solar cells (DSCs). The polymer/TiO2 composite photoelectrode has a structure similar to that of a fiber-reinforced composite; the matrix of the composite photoelectrode contains TiO2 nanoparticles, and PVDF nanofibers are embedded in this matrix. Compared to conventional DSCs, composite-based DSCs show outstanding bending stability because the polymer nanofibers prevent delamination of the electrode by relieving the external stress and effectively retarding crack generation and propagation. Moreover, the efficiency of the cell containing composite electrodes is comparable to that of a cell containing only TiO2, suggesting that the proposed PVDF-nanofiber-reinforced photoelectrode is a promising candidate for a bendable photoelectrode in high-efficiency flexible plastic DSCs.