The enzymatic acylation of (RS)-phenylethylamine with different acyl donors catalysed by lipases, was studied in organic solvents with different hydrophobicities and in mixtures with ionic liquids ((ILs); [BMIm][BF(4)], [BMIm][SCN], [BMIm][Cl] and [BMIm][PF(6)]). Using lipases from Candida antarctica B (CAL-B) and from Aspergillus niger higher conversion degrees and E-values were obtained with ethyl acetate as the acyl donor. When CAL-B was used as the biocatalyst, in a two-phase system formed by [BMIm][X]/dichloromethane or [BMIm][X]/chloroform, the selectivity was better than that obtained in pure organic solvents. The selectivity was found to be related to individual anions in ILs. In this reaction, the ion effectiveness in enhancing the enzyme selectivity followed the series: Cl(-) > SCN(-) > BF(4)(-) > PF(6)(-) in mixtures with dichloromethane, and PF(6)(-) > BF(4)(-) > SCN(-) > Cl(-) in mixtures with chloroform. (C) 2009 Elsevier Ltd. All rights reserved.