Investigations on metal-organic frameworks (MOFs) as direct catalysts have been well documented, but direct catalysis of the chemical conversion of terminal alkynes and CO2 as chemical feedstock by MOFs into valuable chemical products has never been reported. We report here two cluster-based MOFs I and II assembled from a multinuclear Gd-cluster and Cu-cluster, displaying high thermal and solvent stabilities. I and II as heterogeneous catalysts possess active catalytic centers [Cu12I12] and [Cu3I2], respectively, exhibiting excellent catalytic performance in the carboxylation reactions of CO2 with 14 kinds of terminal alkynes under 1 atm and mild conditions. For the first time catalysis of the carboxylation reaction of terminal alkynes with CO2 by MOF materials without any cocatalyst/additive is reported. This work not only reduces greenhouse gas emission but also provides highly valuable materials, opening a wide space in seeking recoverable catalysts to accelerate the chemical conversion of CO2.