Abstract A variety of pyridinecarboxaldehydes are shown to give condensation products in high yields (80–99%, 10 examples) by reacting with benzene and CF 3 SO 3 H (triflic acid). In the superacidic solution, pyridinecarboxaldehydes can react with deactivated arenes ( o -dichlorobenzene and nitrobenzene) and with saturated hydrocarbons (methylcyclohexane and adamantane). Dicationic intermediates from pyridinecarboxaldehydes in superacid (FSO 3 H–SbF 5 ) have been directly observed using low temperature 13 C NMR spectroscopy. Diprotonated pyridinecarboxaldehydes have also been studies using ab initio computational methods.