Photorechargeable supercapacitors are perfect energy storage devices, particularly for solar cells that output electricity only during sunshine hours. The lower energy density of supercapacitors is due to fewer redox‐active sites, poor electrolyte accessibility at the electrodes, and charge loss during charge transfer from solar cells to the supercapacitor. Here, an electrolyte‐accessible organic–inorganic hybrid electrode with synergistic pseudocapacitance of Ti3C2Tx and high theoretical specific capacity CO active centers to enhance the energy density of the supercapacitor is proposed. Density functional theory (DFT) calculations show that the covalent cross‐linking of organic molecules changes the charge density redistribution of Ti3C2Tx, enhances ion absorption and storage, and increases the energy density of the supercapacitors. Based on these DFT calculation results, hybrid electrodes are successfully prepared using p‐phenylene diisocyanate to covalently cross‐link pseudocapacitors Ti3C2Tx with anthraquinone such as 1‐hydroxyanthraquinone (HA) or 1‐amino‐4‐bromoanthraquinone‐2‐sodium sulfonate (ABS). The Ti3C2Tx‐HA hybrid electrodes exhibit high areal specific capacity (2532.5 mF cm−2), excellent ion absorption storage capability, and long‐term stability. The asymmetric supercapacitor yields a decent area specific capacity (1686.72 mF cm−2 at 0.25 mA cm−2) and energy density (599.72 mWh cm−2 at a power density of 200 mW cm−2). These high‐energy‐density supercapacitors are coupled with perovskite solar cells to prepare photorechargeable supercapacitors with fast energy storage.

The photo‐rechargeable supercapacitor enables the self‐powering of flexible wearable electronics. However, flexible wearable electronics require supercapacitors not only with excellent flexibility but also with high energy density. P‐diaminoazobenzene (P‐Azo) as a new type of organic electrode material with NN is directly connected to the benzene ring and forms a large π‐conjugated system, which makes it have a lower lowest unoccupied molecular orbital (LUMO) energy level, is beneficial to transfer of electrons, and increases the conductivity of organic molecules. In addition, NN can realize the transfer of two electrons, which makes P‐Azo have a higher energy density. Asymmetric flexible supercapacitors are fabricated by assembling P‐Azo, activated carbon, and an adhesive electrolyte, with 425.2 mW h cm−2 (55.19 Wh kg−1) energy density at a power density of 80 mW cm−2 (10.38 W kg−1), and 90.7% capacitance retention after 80 000 cycles of bending. In this work, supercapacitors and perovskite submodules are coupled to prepare a photo‐rechargeable supercapacitor to achieve a 7% overall energy‐conversion efficiency. Therefore, this supercapacitor paves a practical route for powering future wearable electronics.