ZnZrOx　solid　solution　is　a　promising　catalyst　for　the　hydrogenation　of　CO2　to　methanol,　but　precise　design　of　the　nanostructure　to　enhance　catalytic　performance　remains　a　significant　challenge.　Herein,　a　ZnZrOx-based　solid　solution　(ZnZrOx-MD)　nanoparticle　catalyst　with　uniform　metal　dispersion　and　remarkable　CO2　activation　ability　was　developed　via　calcination　of　metal-organic　frameworks　[MOFs,　viz.,　PCN-223(Zn)]　with　mixed　metal　(Zr　and　Zn)　as　solid　precursors.　It　was　found　that　the　ZnZrOx-MD　nanoparticle　catalyst　outperformed　its　counterparts　prepared　using　a　traditional　deposition-precipitation　method　(ZnZrOx-TD).　Furthermore,　the　effects　of　the　micromorphology　and　crystal　composition　on　the　catalytic　performance　of　ZnZrOx-MD　were　systematically　investigated.　Comprehensive　characterization　results　reveal　that　ZnZrOx-MD　contained　abundant　oxygen　vacancies,　large　specific　surface　area,　and　uniform　metal　dispersion,　which　collectively　contributed　to　its　excellent　CO2　hydrogenation　performance,　resulting　in　a　high　methanol　selectivity　of　77.2%　at　320　°C.　In　situ　DRIFTS　experiments　confirm　the　mechanism　for　the　CO2　hydrogenation　to　methanol　over　the　ZnZrOx　nanoparticle　catalysts　involved　the　initial　formation　of　HCOO*　species,　followed　by　subsequent　hydrogenation　to　generate　CH3O*　and　ultimately　produce　methanol.　Overall,　this　work　highlights　the　potential　benefits　of　MOFs　as　thermal　decomposition　precursors　for　the　fabrication　of　solid-state　catalysts　with　unique　properties.　©　2024　American　Chemical　Society