For the use in all-plastic flexible dye-sensitized solar cells (DSSCs), various TiO2 photoanodes having different structures were prepared using commercial P25 and ST41 powders. The photoanodes were deposited using an electrophoretic deposition (EPD) technique, followed by a mechanical compression. The deposition kinetics of the EPD photoanode formation was first studied. Based on the deposition kinetics, various photoanode structures consisting of P25, ST41, or a mixture of P25 and ST41 powders were made and characterized. The photoanodes were then evaluated for use in all-plastic flexible DSSCs. The effect of the photoanode structure on the cell performance, including electron transport property, was investigated and discussed. Optimized photoanode structure is reported as a result.