Interconnected macroporous imidazolium-based monoliths are produced via the modified Radziszewski multicomponent reaction (MCR) applied to triamines under high internal phase emulsion (HIPE) conditions. This straightforward one-pot synthesis combines the efficiency and versatility of MCRs with the ease of implementation of the emulsion templating polymerization process. The characterization of the chemical structure and morphology of the resulting materials confirms the formation of the expected macroporous poly(ionic liquid)s (PILs) networks. The promising catalytic activity and recyclability of these porous PIL monoliths are illustrated for the transesterification reaction and the decarboxylation of caffeic acid. In these cases, almost complete conversion is reached while benefiting from the advantages associated with a heterogeneous catalyst.