Photo-supercapacitors (PSCs) combine functions of energy harvesting and storage in a single device, and in this study, a new architecture for a PSC is designed and implemented. Cadmium sulfide (CdS) quantum dots/hibiscus (hb) dye co-sensitized TiO2 is used as the solar cell. Poly(3,4-ethylenedioxypyrrole) (PEDOP)@manganese dioxide (MnO2) is employed as the counter electrode (CE) for the solar cell and also as the electrodes for the symmetric supercapacitor. The two ends of a long flat current collector support two spatially separated PEDOP@MnO2 coatings, which serve as the CEs for the TiO2/hb/CdS photoanode and yet another PEDOP@MnO2 electrode in sandwich configurations. In this cell, under 1 sun (100 mW cm-2) illumination, the TiO2/hb/CdS photoanode undergoes charge separation and by channeling the photocurrent to the PEDOP@MnO2 electrodes, the symmetric cell part is charged to a voltage of 0.72 V. The PSC delivers a specific capacitance of 183 F g-1, an energy density of 13.2 Wh kg-1, and a power density of 360 W kg-1 at a discharge current density of 1 A g-1. During the self-discharge process, PEDOP@MnO2-based PSC retains a voltage of 0.72 V up to 500 s and maintains a stable voltage of 0.5 V thereafter. The TiO2/hb/CdS photoanode with the PEDOP@MnO2 CE in an aqueous polysulfide-silica gel electrolyte delivers a power conversion efficiency of 6.11%. This demonstration of a novel PSC opens up opportunities to develop new architectures for efficiently combining energy conversion and storage. © 2018 American Chemical Society.