Three new manganese-based metal−organic frame-, and [Mn 2 (L) 2 (DMF) 2 (H 2 O)]• 3DMF (3), have been synthesized with the ligand H 2 L (Nphenyl-N′-phenylbicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide dicarboxylic acid). The secondary building units (SBUs) of the Mn-MOFs are controlled by changing the anions of the manganese salts, and the structures are modified from two-fold interpenetrating to non-interpenetrating by adjusting the mixed solvent systems. Along with the structural modification of the Mn-MOFs, we optimized their catalytic activities for the reaction of CO 2 and epoxides toward cyclic carbonates. Both the activity and reusability of the Mn-MOFs are successfully improved in the solvent-free cycloaddition of CO 2 with various epoxides under the mild conditions of atmospheric pressure and 70 °C.