Sample preparation is a critical step that partly determines the sensitivity and accuracy of the whole analytical method. Electromembrane extraction (EME) is one of the most promising sample preparation techniques because of its unique characteristics including high efficiency and selectivity, remarkable sample clean-up ability, potential for automation and eco-friendly merit. Since it was introduced in 2006, EME has been drawing increasing attention. With the growing fundamental studies for performance improvement, EME has been widely applied in various samples and target analytes. In this paper, critical review articles on EME are summarized and an overall picture of EME is depicted, from fundamental theories to experimental aspects and then different modes of applications. Finally, future research directions and highlights are discussed based on the current studies and authors’ work experience. We believe that this comprehensive overview will provide a firm foundation for researchers in concerning fields and inspire more works for EME development