An in-line coupling of a micro-membrane extraction unit, based on supported liquid membrane, with commercially available capillary electrophoresis equipment is described. A main characteristic of this micro-membrane device, made from a simple Eppendorf tube, is that it permits the application of voltage in the acceptor solution to be applied during the extraction process. This has been shown as an alternative to enhance sensitivity, as the analytical signal achieved by applying 10 kV for 20 min was similar to that obtained without the application of voltage and with extraction time of 60 min. In addition, the design has been made permitting both in-line hydrodynamic and electrokinetic sample introduction into the electrophoretic capillary. The analytical potential of the proposed system has been demonstrated by the direct determination of nitroimidazoles from pig liver tissue. The high efficiency of the proposed system allowed the extraction and the determination of the analytes to be performed from a simple tissue homogenate obtained in water. The precision of the analysis of spiked samples, expressed in terms of relative standard deviation, was better than 4.8%.