The applicability of cellulose acetate membranes (CAMs) as a solid matrix for the luminescence determination of pyrene in aqueous micellar solutions is shown. The effect of the concentrations of various surfactants, namely, anionic sodium dodecyl sulfate (SDS), cationic cetyltrimethylammonium bromide (CTAB), and nonionic polyoxyethylene (10) mono-4-isooctyl phenyl ether (TX-100), on the fluorescence of pyrene in aqueous micellar solutions before and after sorption preconcentration and in an adsorbed state on a CAM has been studied. It has been found that the fluorescence intensity of pyrene on the solid-phase matrix increases as a result of pyrene solubilization in surfactant hemimiceles formed on the sorbent surface. The highest degree of pyrene extraction on CAMs has been achieved in the presence of cationic CTAB micelles. The CAM has a negative surface potential (-31.5 +/- 2.5 mV), which affects the hydrocarbon recovery. The degree of extractlion and the polarity index of a microenvironment of pyrene molecules in solutions decrease in the order CTAB -> SDS -> TX-100.