Brønsted acidic ionic liquids (BAILs) have been used as catalyst and solvent in organic synthesis, due to their negligible volatility, remarkable solubility, good catalytic activity, and easily structurally tunable properties. In the present study, we have investigated the catalytic efficiency of economically viable ionic liquids bearing different cations pyridinium ([PyH]+ and triethylammonium [TEAH]+) for the esterification of aromatic acid with various aliphatic alcohols and crossed aldol condensation of aromatic aldehydes with cyclohexanone under ambient condition. We also examined the effect of various process parameters on the yield of aromatic esters and α,α’-bis(arylidene)cycloalkanones. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim