This work demonstrates the feasibility of constructing near-infrared-responsive photocatalysts for the efficient activation and selective conversion of CH₄ under full-solar-spectrum illumination. Moreover, the authors reveal the key roles of photogenerated holes and O₂²⁻ species in enhancing both the activity and selectivity while suppressing CH₄ overoxidation and by-product formation. The findings can provide valuable insights for developing scalable, solar energy-driven technologies for the sustainable utilization of CH₄.