Using silver ions as carrier in oil/water/oil-type emulsion liquid membranes, batch wise extraction experiments were carried out to separate toluene from a mixture of toluene and n-heptane. The separation performances, represented by the permeation rate, emulsion stability, and separation factor, were analyzed systematically by varying the operating parameters, viz., contact time, concentration of Ag+, emulsification time, surfactant concentration, membrane stabilizer concentration, relative amount of solvent, and initial feed phase concentration. The emulsion liquid membranes thus formed are stable, and Ag+ and surfactant concentrations strongly affect the permeation behavior of toluene.