N-octyl- and N-decylsubstituted N-methylimidazolium saccharinates ([C(8/10)C(1)im][Sac]) were synthesized and found to form biphasic systems after saturation with water. Therefore, they could be considered as hydrophobic ionic liquids (ILs), which suggests their potential application as extraction media. The performance of these ILs as extractants of L-lactic acid (LA) from aqueous solutions was evaluated. The pH dependence and the influence of additives such as kosmotropic salts or alcohols on the LA extraction yield (En) were comprehensively studied. As a result, EY = 90% was achieved with [C(8)C(1)im][Sac] in two extraction steps. Furthermore, based on the observed effects of pH and kosmotropic salt, successful LA re-extraction (95%) from the IL-rich phase was attained by means of K2HPO4-stripping solution. The latter represents the highest re-extraction efficiency for LA/IL system described so far in the literature. Based on the results obtained, a plausible mechanism of LA extraction, which considers the secondary structure of the water saturated long side chain imidazolium saccharinates, is proposed. As a result, the IL extraction capacity was attributed to the formation of polar channels, separated by non-polar domains, which channels are capable of swelling and liberating water and other hydrophilic solutes. (C) 2014 Elsevier B.V. All rights reserved.