Two highly stable isoreticular metal-organic frameworks comprising chains of zirconium coordinated with linkers of 1,4-H2BDC (1,4-benzenedicarboxylic acid) and 4,4'-H2BPDC (4,4'-biphenyldicarboxylic acid), denoted as MIL-140A and MIL-140C, were synthesized. The catalytic activity of these frameworks was studied for the coupling reaction of CO2 and epoxides to produce cyclic carbonates under solvent-free conditions. Excellent activity was observed for both catalysts: they yielded high epoxide conversion with >99% selectivity toward the cyclic carbonate, and were fully reusable even after four cycles without any considerable loss of initial activity. The enhancement in the catalytic activity was explained based on acidity/basicity studies. The influence of various reaction parameters such as catalyst amount, reaction time, reaction temperature, and CO2 pressure was also investigated. Reaction mechanism was proposed on the basis of experimental evidence and our previous DFT (density functional theory) studies.