Metal-organic　frameworks　(MOFs),　as　an　emerging　class　of　porous　materials,　demonstrated　substantial　potential　for　applications　in　chemical　engineering　processes.　However,　their　production　often　generates　significant　waste　including　ionic　residues　and　organic　solvents,　posing　considerable　environmental　concerns.　Herein,　we　report　the　environmentally　benign　MOF　synthesis　with　metal　oxides　precursors,　yielding　water　as　the　exclusive　by-product.　This　approach　not　only　enhances　atom　economy　but　also　promotes　solvent　recycling　by　preventing　anion　accumulation,　significantly　reducing　waste　generation.　The　synthesis　can　be　easily　scaled　up　in　a　10-L　reactor　with　an　impressive　space-time　yield　of　608　kgm-3day-1.　Furthermore,　MOF-76(Y)　was　implemented　in　a　reactor　for　catalytic　cycloaddition　reaction　at　kg-scale.　Through　optimization　of　the　interfacial　contact　between　CO2　and　the　reaction　liquid　phase,　a　yield　of　96.7%　was　achieved　under　mild　conditions.　This　work　demonstrates　a　rare　example　of　scalable　and　sustainable　synthesis　of　MOF　materials　coupled　with　catalysis　implementation　at　kilogram　scale.