Rechargeable aqueous iodine‐based electrochemical energy storage systems offer a cost‐effective alternative to conventional alkali metal batteries for grid‐scale applications. However, their practical deployment is hindered by sluggish iodine redox kinetics and the shuttle of polyiodides, which severely limit their lifespan. To address these challenges, a novel solid‐state organic||I ₂ battery leveraging a Co ₃ O ₄ ‐TiO ₂ heterojunction photocathode is developed. By integrating a photo‐assisted mechanism with an innovative device architecture, the system achieves accelerated iodine conversion kinetics, enhances iodide ion utilization, and enables a four‐electron redox pathway. Theoretical calculation combined with electrochemical analysis reveals that the photo‐assisted mechanism promotes electrostatic adsorption of polyiodides, accelerates interfacial charge transfer, and significantly improves iodine redox kinetics. As a result, the organic||I ₂ battery delivers a high specific capacity of 1.36 mAh cm ⁻² , a discharge voltage of 2.4 V, and excellent cycle stability over 1000 cycles, retaining 80.9% of its capacity at a current density of 10 mA cm ⁻² . This photo‐enhanced battery exhibits strong competitiveness compared to previously reported iodine‐based batteries. The remarkable performance of this photo‐assisted prototype offers a sustainable and cost‐effective solution for next‐generation energy storage.

Carbon aerogels synthesized via the polymerization of resorcinol (R) and formaldehyde (F) exhibit remarkable physiochemical properties, such as high thermal stability and excellent electrical conductivity. However, their limited specific surface area and porosity restrict their application potential. Herein, we developed hierarchical porous carbon aerogels using a one-step carbonization and activation method, directly converting the resin into carbon aerogel material by adding KOH as an activating agent. In contrast to conventional carbon aerogels with an irregular block ground structure, our hierarchical porous carbon aerogels exhibit substantially enhanced specific surface area, total pore volume, and surface oxygen content. In addition, this straightforward one-step fabrication approach holds significant promise for energy storage applications. Notably, the hierarchical porous carbon aerogel C1, with a KOH/RF mass ratio of 1, was proven to be the most effective electrode candidates, achieving a specific capacitance of 261.9 F·g⁻¹ at 1 A·g⁻¹ and 208.2 F·g⁻¹ at 20 A·g⁻¹. Moreover, it exhibited an outstanding rate capability of 79.5% and excellent capacity retention of approximately 97.5% after 10,000 cycles (7 A·g⁻¹). This work highlights a promising approach for synthesizing commercial-grade carbon aerogels with hierarchical porosity, enabling high-performance energy storage applications.