The　photocatalytic　nonoxidative　coupling　of　methane　(CH4)　is　crucial　for　sustainable　energy　production　and　chemical　synthesis,　however,　a　key　challenge　in　advancing　this　process　lies　in　the　development　of　efficient　and　highly　selective　catalytic　systems.　In　this　study,　we　employ　an　in　situ　thermally　induced　strategy　to　promote　the　in-situ　growth　of　oxygen　vacancies　(VO)　for　constructing　a　high-density　In-VO-In-OH　frustrated　Lewis　pairs　(FLP)　on　Ag/In(OH)3-InOOH　(Ag/InOxHy).　Our　results　demonstrate　that　FLP　can　effectively　polarize　C–H　bonds,　while　Ag　nanoparticles　serve　as　electron　acceptors,　significantly　reducing　the　recombination　of　photogenerated　carriers　and　enhancing　the　catalytic　performance　of　methane　coupling.　Benefiting　from　the　high　density　of　FLP　and　photothermal　synergistic　effect,　we　achieve　a　remarkable　C2H6　yield　of　339.2　μmol　gcat−1h−1　over　Ag/InOxHy　in　a　flow　methane　atmosphere.　Notably,　in-situ　electron　paramagnetic　resonance　analysis　not　only　validates　this　innovative　strategy　but　also　reveals　a　new　mechanism　of　oxygen　vacancy　recycling　which　showcases　its　great　potential　to　advance　other　photocatalytic　processes.　©　2025　Elsevier　Inc.