The feasibility of using sulfur-containing organophosphorus reagents for the chelation-supercritical fluid extraction (SFE) of toxic heavy metals and uranium from acidic media was investigated. The SFE experiments were conducted in a specially designed flow-through liquid extractor. Effective extraction of the metal ions from various acidic media was demonstrated. The effect of the ligand concentration in supercritical CO2 on the kinetics of metal extraction was studied. A simplified model is used to describe the extraction kinetics, and good agreement of experimental data with the equilibrium-based model is achieved.