AbstractPhoto‐driven CH₄ conversion to multi‐carbon products and H₂ is attractive but challenging, and the development of efficient catalytic systems is critical. Herein, we construct a solar‐energy‐driven redox cycle for combining CH₄ conversion and H₂ production using iron ions. A photo‐driven iron‐induced reaction system was developed, which is efficient at selective coupling of CH₄ as well as conversion of benzene and cyclohexane under mild conditions. For CH₄ conversion, 94 % C₂ selectivity and a C₂H₆ formation rate of 8.4 μmol h⁻¹ is achieved. Mechanistic studies reveal that CH₄ coupling is induced by hydroxyl radical, which is generated by photo‐driven intermolecular charge migration of an Fe³⁺ complex. The delicate coordination structure of the [Fe(H₂O)₅OH]²⁺ complex ensures selective C−H bond activation and C−C coupling of CH₄. The produced Fe²⁺ can be used to reduce the potential for electrolytic H₂ production, and then turns back into Fe³⁺, forming an energy‐saving and sustainable recyclable system.