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Brønsted acidic ionic liquids (ILs) have been synthesized and investigated as catalysts in esterification and transesterification reactions: simple and non-corrosive salts characterized by aliphatic cations associated with an “acidic” anion (in particular, [HSO4]−) gave the higher yields. A quite good correlation between IL acidity (H0) and catalytic ability was found although also the hydrophilic nature of the ionic medium probably affects the process efficiency.