DLLME was firstly introduced by Assadi and co-workers in 2006 [23], which is an improved LLE method based on the use of microliter volumes of extraction solvent. Its applications in various matrices such as cosmetics [9], fruits and vegetables [24], food and environmental samples [25–27] have been widely reviewed. How- ever, DLLME usually suffers from two obvious drawbacks. Firstly, it generally requires high-density solvents such as chloroform, carbon tetrachloride, tetrachloroethane or chlorobenzene, which are highly toxic and environmentally unfriendly, and may limit its applicability. For these halogenated hydrocarbons, their GC peaks partially overlap with those of some analytes. Secondly, there is a lack of compatibility between the extraction solvents and detect- ing instruments such as reverse-phase HPLC [25] and IC [28]. Lighter-than-water organic solvents [20,26] and ionic liquids [29] are lately introduced as extraction solvents to overcome these inherent limitations. The performance of DLLME in the extraction of organic compounds from simple matrices like aqueous samples has proved to be excellent, but it is not yet perfect in complex matrices including cosmetic samples. Therefore, it needs further improvement.