The present work has for the first time compared extraction of basic analytes across a supported liquid membrane (SLM) based on (1) passive diffusion in a pH gradient sustained over the SLM and (2) electrokinetic migration in an electrical field sustained over the SLM. For the passive diffusion experiments, performed as liquid-phase microextraction (LPME), five basic drugs were extracted under strong agitation from alkaline samples (10 mM NaOH), through 2-nitrophenyl octylether immobilized in the pores of a porous hollow fibre of polypropylene (SLM), and into 25 μl of 10 mM HCl as the acceptor solution. The experiments based on electrokinetic migration, performed as electro membrane isolation (EMI), were conducted under strong agitation from acidic samples (10 mM HCl), through the same SLM as in LPME, and into 25 μl of 10 mM HCl as the acceptor solution. Whereas LPME relied on diffusion and to some extent also convection as the principal mechanisms of mass transfer, mass transfer in EMI also included a strong contribution from electrokinetic migration. Thus, extraction kinetics was improved by a factor between 6 and 17 utilizing EMI instead of LPME. This major difference in terms of speed was especially pronounced from small sample volumes (150 μl), and suggest that EMI may be a very interesting future concept for miniaturized sample preparation. In addition to improved extraction kinetics, extraction rates were strongly compound dependent in EMI, opening the possibility to control the extraction selectivity by the extraction time.