Ag-doped TiO2/PVA nanofibers have many potential applications as a photoanode of dye-sensitized solar cells (DSSCs). In this study, we report the fabrication of DSSCs based on Ag-doped TiO2/PVA nanofibers as photoanode, graphene oxide as a Pt-free counter electrode catalyst, and natural dye sensitizer. Ag-doped TiO2/PVA nanofibers were fabricated using an electrospinning method. The electrospun nanofibers were characterized by a scanning electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The nanoparticle content of lower 100 mg/mL, and the electrospun nanofibers were uniform. Based on the results of the characterization analysis, the electrospun Ag-doped TiO2/PVA nanofibers were successfully prepared with diameters from 100 to 400 nm. They were used as photoanodes of DSSCs using a natural dye sensitizer extracted from the leaf of the magenta plant. The highest power conversion efficiency of DSSCs with Ag-doped TiO2/PVA nanofibers was 0.6% from the J-V curves. This approach would be a potential application for fabricating a solar cell based on composite fiber, Pt-free catalyst, and natural dye sensitizer.