This article was aimed to investigate the cadmium extraction behaviors of the two different polyvinyl chloride membranes incorporating Aliquat 336-electrospinning and film-casting. An optimal investigation condition for membranes used in the extraction process was produced at 25 kV with 10 cm tip-to-collector distance. Membranes were electrospun for 8 h at 200 mu L/h. Membrane extraction studies were carried out using a 127 mg/L Cd(II) solution. Scanning electron microscope (SEM) images revealed differences in fiber diameters and membrane morphology. The addition of Aliquat produced very fine fibers (7-722 nm) resulting Brunauer-Emmett-Teller (BET) surface areas of 4.67-11.3 m(2)/g for electrospun membranes and 1.70-5.44 m(2)/g for film-casted membranes. Extraction studies using membranes with different levels of Aliquat (0-40% w/w) revealed that the cadmium extraction performance of electrospun membranes was significantly better than conventional film-cast membranes. For 40% Aliquat 336, with an initial concentration of 127 mg/L Cd, the cast membrane extracted down to concentration to 115 mg/L as compared to electrospun membrane, which extracted down to 88 mg/L within 40 h. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121: 327-335, 2011