A bifunctional surfactant was used as a carrier of penicillin G for its continuous extraction by an emulsion liquid membrane without an extractant in a countercurrent extraction column of Oldshue-Rushton type. A permeation model was presented to describe transport mechanism of penicillin G in the continuous extraction system, including an axial dispersion model for the continuous phase and a mass transfer model for the dispersed emulsion phase. The mass transfer model describes the external mass transfer around the emulsion drop, the reaction at the external interface, the diffusion as well as the reaction equilibrium within the w/o emulsion drop, and the pH change of internal aqueous phase. Here, we considered three experimental variables: penicillin G concentration, pH of continuous phase and surfactant concentration. The calculated results from the permeation model fitted the experimental data well.