This　work　demonstrates　the　long-range　redox　reactivity　of　gold　plasmon-generated　hot　electrons　for　solar-driven　CO2　conversion.　A　series　of　Au　NR@ZnO　core-shell　photocatalysts　with　a　tunable　shell　thickness　are　rationally　designed　to　achieve　the　solar-to-CH4　conversion,　where　the　hot　plasmonic　electrons-induced　photoreduction　takes　place　on　the　polar　oxide　moiety.　The　shell　thickness-independent　activity　implies　that　the　core,　gold　nanorods,　plays　a　dominant　role　in　the　CH4　generation.　The　ZnO　metal　oxide　semiconductor　shell　is　beneficial　to　prolong　the　lifetime　of　hot　electrons,　thereby　enhancing　the　photocatalytic　efficiency.　However,　the　thickness　of　ZnO　shell　is　not　relevant　to　the　production　rate.　Both　of　these　two　parts　are　co-excited　by　solar　light　and　synergetic　enhance　the　photocatalytic　activity.　©　2020　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim