In this work, three bifunctional metal‐organic frameworks (MOFs) were constructed through the introduction of various linear amine functional groups within MIL‐101(Cr). The unsaturated chromium metal center was incorporated with three various ligands including ethylene diamine, diethylene triamine, and diamino butane. The resultant prepared MOFs contain unsaturated chromium centers as Lewis acidic centers and amine groups as basic sites. The contemporary existence of basic and acidic centers allowed prepared bifunctional compounds to be highly effectual heterogeneous catalysts for chemical fixation of CO2 with epoxides, affording cyclic carbonates, under relatively mild conditions and in the absence of either solvent or cocatalyst. High tendency of prepared structures toward CO2 adsorption followed by speeding up the nucleophilic attack resulted in gaining excellent conversion, selectivity, and activity for large epoxide as well as bulky ones. The synthesized catalyst outperforms other reported heterogeneous catalysts. High conversion, TON, recyclability, and mild reaction conditions are some distinctive characteristics of the bifunctional synergetic catalysts.