Dye-sensitized solar cells (DSSCs), a powerful system to convert solar energy into electrical energy, suffer from the high cost of the Pt counter electrode and photosensitizer. In this study, the dual application of waste grape skin is realized by employing the grape skin and its extract as the carbon source of the carbon-based counter electrode and photosensitizer, respectively. The ultraviolet–visible absorption and Fourier transform infrared spectroscopy verify the strong binding between the dye molecules (anthocyanins) in the extract and the TiO2 nanostructure on the photoanode, contributing to a high open-circuit voltage (VOC) value of 0.48 V for the assembled DSSC device. Moreover, the waste grape skin was subjected to pyrolysis and KOH activation and the resultant KOH-activated grape skin-derived carbon (KA-GSDC) possesses a large surface area (620.79 m2 g−1) and hierarchical porous structure, leading to a high short circuit current density (JSC) value of 1.52 mA cm−2. Additionally, the electrochemical impedance spectroscopy reveals the efficient electron transfer between the electrocatalyst and the redox couples and the slow recombination of electrolytic cations and the photo-induced electrons in the conduction band of TiO2. These merits endow the DSSC with a high photovoltaic efficiency of 0.48%, which is 33% higher than that of a common Pt-based DSSC (0.36%). The efficiency is also competitive, compared with some congeneric DSSCs based on other natural dyes and Pt counter electrode. The result confirms the feasibility of achieving the high-value application of waste grape skin in DSSCs.