1,3-Disulfonic acid imidazolium carboxylate [DSIM][X] (where X = [CH3COO]−, [CCl3COO]−, [CF3COO]−) ILs were synthesized and their catalytic activity examined for the preparation of 14H-dibenzo[a,j]xanthene and 1,8-dioxo-decahydroacridine derivatives under solvent-free conditions and in water at 80–100 °C.