Abstract New heterocyclic ring systems consisting of (±) methanodibenzodiazocine and imidazolium/ benzimidazolium salts were synthesized in very good yield. Subsequently, these halide salts were subjected to the anion exchange reaction with KPF6 to yield the corresponding azolium salts in excellent yield. The possible applications of these newly prepared salts were investigated in homogeneous catalysis. Remarkable changes in the catalytic activity were observed by varying the bulkiness of N-substituent at imidazole. Catalytic activity of these newly prepared salts was tested for the benzoin condensation reaction. Exclusive formation of benzoin products were observed in good yield. Similarly, the dimerization of cyclohexen-1-one to Baylis-Hillman type product, 2-(3-oxocyclohexyl)-2-cyclohexen-1-one was studied. [Figure not available: see fulltext.] © 2015 Indian Academy of Sciences.