In hollow fiber membrane liquid-phase microextraction (LPME), target analytes are extracted from aqueous samples and into a supported liquid membrane (SLM) sustained in the pores in the wall of a small porous hollow fiber, and further into an acceptor phase present inside the lumen of the hollow fiber. The acceptor phase can be organic, providing a two-phase extraction system compatible with capillary gas chromatography, or the acceptor phase can be aqueous resulting in a three-phase system compatible with high-performance liquid chromatography or capillary electrophoresis. Due to high enrichment, efficient sample clean-up, and the low consumption of organic solvent, substantial interest has been devoted to LPME in recent years. This paper reviews important applications of LPME with special focus on bioanalytical and environmental chemistry, and also covers a new possible direction for LPME namely electromembrane extraction, where analytes are extracted through the SLM and into the acceptor phase by the application of electrical potentials.