The　selective　oxidation　of　methane　to　value-added　chemicals　under　mild　conditions　presents　a　sustainable　yet　challenging　route,　hindered　by　sluggish　CH4　activation　and　overoxidation.　Herein,　we　report　a　delicate　strategy　combining　Ti　doping　and　Au　loading　to　construct　a　high-performance　Au/Ti-CeO2　photocatalyst　for　ethane　production　from　oxidative　methane　coupling.　The　optimized　catalyst　achieves　a　C2H6　production　rate　of　2971.4　μmol　g−1　h−1　with　85.1　%　C2+　selectivity,　stably　operating　over　20　reaction　cycles.　In　situ　X-ray　photoelectron　spectroscopy,　electron　paramagnetic　resonance,　and　diffuse　reflectance　infrared　Fourier　transform　spectroscopy　analyses　reveal　that　Ti　doping　introduces　impurity　energy　levels　into　CeO2,　promoting　directional　electron　migration　to　surface　Au　nanoparticles　(NPs)　via　a　built-in　electric　field.　The　Au　NPs　act　as　electron　accumulation　sites　to　activate　O2,　facilitate　∗CH3　radical　coupling　into　C2H6,　and　stabilize　reactive　intermediates,　thus　enhancing　charge　separation　and　suppressing　intermediate　overoxidation.　This　study　highlights　the　significance　of　synergistic　modulation　via　elemental　doping　and　cocatalyst　engineering　in　tuning　charge　dynamics　and　surface　reactivity　for　efficient　photocatalytic　methane　conversion.　©　2025　College　of　Chemistry　and　Molecular　Engineering,　Peking　University