A series of di-cationic styrene-functionalized imidazolium-based salts in which the two imidazolium rings are bridged by a functionalized spacer were prepared. The salts were polymerized to afford cross-linked imidazolium-based ionic polystyrene materials which, due to the presence of the functionalized spaces, should be highly active organocatalysts for the cycloaddition of CO2 to epoxides to afford cyclic carbonates (CCE reaction). Consequently, the catalytic activity of the polymers was evaluated in the CCE reaction. The most active catalyst incorporates a diol functionality and is active at 80 °C and 4 bars at a loading of 5 mol%, which is comparable to the most active organocatalysts. Moreover, high yields can be obtained under atmospheric pressure when the temperature is increased to 120 °C. Under more forcing conditions the catalyst is highly active at a loading one order of magnitude lower and highlights the importance of benchmark conditions for the CCE reaction. Moreover, the polymer catalysts are advantageous as they can be used at low catalyst loadings, the carbonate product is easily isolated in pure form, and loss of activity of the recovered polymer catalyst is not observed during reuse.