Despite　suffering　from　slow　charge-carrier　mobility,　photocatalysis　is　still　an　attractive　and　promising　technology　toward　producing　green　fuels　from　solar　energy.　An　effective　approach　is　to　design　and　fabricate　advanced　architectural　materials　as　photocatalysts　to　enhance　the　performance　of　semiconductor-based　photocatalytic　systems.　Herein,　metal–organic-framework-derived　hierarchically　ordered　porous　nitrogen　and　carbon　co-doped　ZnO　(N-C-ZnO)　structures　are　developed　as　nanoreactors　with　decorated　CoOx　nanoclusters　for　CO2-to-CO　conversion　driven　by　visible　light.　Introduction　of　hierarchical　nanoarchitectures　with　highly　ordered　interconnected　meso–macroporous　channels　shows　beneficial　properties　for　photocatalytic　reduction　reactions,　including　enhanced　mobility　of　charge　carriers　throughout　the　highly　accessible　framework,　maximized　exposure　of　active　sites,　and　inhibited　recombination　of　photoinduced　charge　carriers.　Density　functional　theory　calculations　further　reveal　the　key　role　of　CoOx　nanoclusters　with　high　affinity　to　CO2　molecules,　and　the　Co-O　bonds　formed　on　the　surface　of　the　composite　exhibit　stronger　charge　redistribution.　As　a　result,　the　obtained　CoOx/N-C-ZnO　demonstrates　enhanced　photocatalysis　performance　in　terms　of　high　CO　yield　and　long-term　stability.　©　2022　Wiley-VCH　GmbH.