A supramolecular solvent (Ss) made up of reverse micelles of 1-decanol in tetrahydrofuran (THF): water was used for the fast and selective microextraction of Cu(II) prior to its determination by microsampling flame atomic absorption spectrometry (FAAS). Cu(II) was complexed with dimethyl dithiocarbamate (DMDC) to obtain hydrophobic complex and extracted to supramolecular solvent phase. The influences of some analytical parameters including pH, type and volume of supramolecular solvent, amount of complexing agent, ultrasonication and centrifuge time and sample volume were investigated. The effects of matrix components were also examined. The detection limit (LOD) and the quantification limit (LOQ) were 0.52 mu g L-1 and 1.71 mu g L-1 respectively. An preconcentration factor was obtained as 60 and the relative standard deviation was <3%. The accuracy of the developed method was evaluated by the analysis of the certified reference materials (TMDA-64.2 water, SRM 1568 A Rice Flour and 8433 Corn Bran) and addition-recovery tests. The presented supramolecular solvent based liquid-liquid microextraction (SsLLME) procedure was applied to the determination of copper in food and water samples with satisfactory results. (C) 2014 Elsevier B.V. All rights reserved.