Light-driven　photoredox　catalysis　presents　a　promising　approach　for　the　activation　and　conversion　of　methane　(CH4)　into　high　value-added　chemicals　under　ambient　conditions.　However,　the　high　C−H　bond　dissociation　energy　of　CH4　and　the　absence　of　well-defined　C−H　activation　sites　on　catalysts　significantly　limit　the　highly　efficient　conversion　of　CH4　toward　multicarbon　(C2+)　hydrocarbons,　particularly　ethylene　(C2H4).　Herein,　we　demonstrate　a　bimetallic　design　of　Ag　nanoparticles　(NPs)　and　Pd　single　atoms　(SAs)　on　ZnO　for　the　cascade　conversion　of　CH4　into　C2H4　with　the　highest　production　rate　compared　with　previous　works.　Mechanistic　studies　reveal　that　the　synergistic　effect　of　Ag　NPs　and　Pd　SAs,　upon　effecting　key　bond-breaking　and　-forming　events,　lowers　the　overall　energy　barrier　of　the　activation　process　of　both　CH4　and　the　resulting　C2H6,　constituting　a　truly　synergistic　catalytic　system　to　facilitate　the　C2H4　generation.　This　work　offers　a　novel　perspective　on　the　advancement　of　photocatalytic　directional　CH4　conversion　toward　high　value-added　C2+　hydrocarbons　through　the　subtle　design　of　bimetallic　cascade　catalyst　strategy.　©　2024　Wiley-VCH　GmbH.