A fast and simple method involving separation and determination of thallium (Tl) species, based on novel ionic liquid-assisted ion pairing dispersive liquid-liquid microextraction (DLLME) method, was developed. Initially, Tl(III) was selectively complexed with chloride ion to form [TlCl4](-) chlorocomplex. Subsequently, tetradecyl(trihexyl)phosphonium chloride ionic liquid (CYPHOS (R) IL 101) was used to form the ion-pair with [TlCl4](-) anion followed by extraction. The DLLME procedure was developed by dispersing 80 mu L. of carbon tetrachloride with 100 mu L of ethanol added to the aqueous solution. After DLLME, the upper aqueous phase containing Tl(I) only was removed and analysed by inductively coupled plasma-mass spectrometry (ICP-MS). In contrast to Tl(III), Tl(I)) species does not form neither stable nor anionic complexes with chloride ions and it was not extracted into the organic phase. Total Tl concentration was obtained by direct introduction of sample into ICP-MS instrument. The calibration graph for the analyte was linear with a correlation coefficient of 0.9989. Under optimal conditions, detection limit of Tl species was 0.4 ng L-1. The relative standard deviation (n = 10) at 1 ng mL(-1) Tl concentration level was 1.3% for Tl(I) and 1.5% for Tl(III). The method was successfully applied for fast speciation analysis of Tl at ultratrace levels in real water samples. (C) 2012 Elsevier B.V. All rights reserved.