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CO2 epoxidation to cyclic carbonates under mild, solvent-free conditions is a promising pathway toward sustainable CO2 utilization. Metal–organic frameworks (MOFs) explored for such applications so far are commonly composed of nonrenewable ligands such as benzene dicarboxylate (BDC) or synthetically complex linkers and therefore are not suitable for commercial utilization. Here, we report new yttrium 2,5-furandicarboxylate (FDC)-based MOFs: “UOW-1” and “UOW-2” synthesized via solvothermal assembly, with the former having a unique structural topology. The FDC linker can be derived from biomass and is a green and sustainable alternative to conventionally used BDC ligands, which are sourced exclusively from fossil fuels. UOW-1, owing to unique coordination unsaturation and a high density of Lewis active sites, promotes a high catalytic activity (∼100% conversion; ∼99% selectivity), a high turnover frequency (70 h–1), and favorable first-order kinetics for CO2 epoxidation reactions using an epichlorohydrin model substrate under solvent-free conditions within 6 h and a minimal cocatalyst amount. A systematic catalytic study was carried out by broadening the epoxide substrate scope to determine the influence of electronic and steric factors on CO2 epoxidation. Accordingly, higher conversion efficiencies were observed for substrates with high electrophilicity on the carbon center and minimal steric bulk. The work presents the first demonstration of sustainable FDC-based MOFs used for efficient CO2 utilization.