Dispersive liquid-liquid microextraction (DLLME) is a novel microextraction technique with a great potential in sample pretreatment, which has been increasingly used for preconcentration of diverse analytes. This review updates the state of the art and discusses promising prospects of DLLME, especially focuses on its combined use with chromatographic techniques for organic compounds analysis in environmental water samples. General and specific concepts of the fundamental theory of DLLME are described, and examples of recent innovations and applications are provided to demonstrate its potential for the determination of a wide range of organic compounds in various water matrices. Moreover, some limitations related to DLLME are also discussed in detail, and an outlook on the future of the technique, specifically its coupling with other pretreatment approaches, separation and detection techniques, is also given.