AbstractDry reforming of methane (DRM) has provided an effective avenue to convert two greenhouse gases, CH4 and CO2, into syngas. Here, we design a DRM photocatalyst Rh/CexWO3 that invokes both photothermal and photoelectric processes, which overcomes the thermodynamic limitation of DRM under conventional conditions. In contrast to plasmonic or UV‐response photocatalysts, our photocatalyst produces a superior light‐to‐chemical energy efficiency (LTCEE) of 4.65 % with a moderate light intensity. We propose that a light‐induced metal‐to‐metal charge transfer plays a crucial role in the DRM reaction, which induces a redox looping between Ce to W species to lower the activation energy. Quantum mechanical studies reveal that a high oxygen mobility of CexWO3, accompanied with the formation of oxo‐bridge species, results in a substantial elimination of deposited C species during the reaction. Our catalyst design strategy could offer a promising energy‐efficient industrial process for DRM.