A supramolecular solvent microextraction procedure was established for the separation/preconcentration of uranium(VI) (U(VI)) prior to its determination by UV-Vis spectrophotometry. 1-(2-Pyridylazo)-2-naphthol (PAN) was used to form a red chelate (U-PAN) with U(VI) at pH 10. U-PAN was extracted by undecanol in tetrahydrofuran. All the parameters that affect extraction efficiency like solution pH, amount of ligand, type and volume of supramolecular solvent, sample volume, and diverse ion effect were optimized. The preconcentration factor was 17. The detection limit was 0.31 mu g L-1. The method was validated using GBW07424 (GSS-10 certified reference material). Microextraction was also applied to water and soil samples.