The extraction of Cephalosporin-C (CPC) from dilute fermentation broth of Cephalosporium acremonium was studied in a bull; liquid membrane as well as in an emulsion liquid membrane system. Aliquat-336 was used as the extracting agent to provide facilitated transport of CPC via liquid-liquid ion exchange mechanism. By maintaining an appropriate pH gradient in the feed and receiving phases, facilitated uphill transport could be achieved in the bulk liquid membrane system. The culture broth contains CPC and deacetyl CPC (DCPC) which are structurally almost similar, but CPC is more hydrophobic in nature. Selective separation of CPC could be achieved in a suitably formulated liquid membrane system. A simple mass transfer model predicts the permeation rate in the bulk liquid membrane. The permeation process in an emulsion liquid membrane appears to be controlled by the aqueous boundary layer resistance and diffusion in the emulsion globule. This is perhaps the first demonstration of the liquid membrane as an effective technique for selective extraction of CPC from fermentation broth of Cephalosporium acremonium.