Electromembrane extraction (EME) is a novel sample preparation technique in pharmaceutical, chemical, clinical and environmental analysis. This technique uses electromigration across artificial liquid membranes for selective extraction of analytes and sample enrichment from complex matrices. This review focuses on the setup, general procedure and parameters affecting the extraction efficiency of EME. An overview of innovations in EME (on-chip EME, low voltage EME, drop-to-drop EME, pulsed EME and EME followed by low-density solvent based ultrasound-assisted emulsification micro-extraction) is also presented in this article and attention is focused on the use of EME for pharmaceutical, chemical, clinical and environmental analysis.