Mild reaction conditions (nearly room temperature and atmospheric CO2 pressure) for the cycloaddition of CO2 with epoxides to produce cyclic carbonates were investigated applying MIL-101(Cr) as a catalyst. The MIL-101 catalyst contains strong acid sites, which promote the ring-opening of the epoxide substrate. Moreover, the high surface area, enabling the adsorption of more CO2 (substrate), combined with a large pore size of the catalyst is essential for the catalytic performance. Additionally, epoxide substrates bearing electron-withdrawing substituents or having a low boiling point demonstrated an excellent conversion towards the cyclic carbonates. MIL-101(Cr) for the cycloaddition of carbon dioxide with epoxides is demonstrated to be a robust and stable catalyst able to be re-used at least five times without loss in activity.