Marked solubility differences of nicotine in the ionic liquids [C(2)mim][NTf(2)], [C(2)mim][EtOSO(3)], and [C(n)mim]Cl, 6 <or= n <or= 10, are observed through the analysis of the corresponding phase diagrams. These show the potential of commonly used ionic liquids to extract and purify this important compound. From a fundamental standpoint, the generally enhanced solubility of nicotine in these ionic liquids as compared to that of aromatic and aliphatic hydrocarbons can be assigned to the presence of the aromatic pyridine ring and the large aliphatic N-methyl-pyrrolidine residue.