Two of the main topics of growing concern in analytical chemistry are the development of green analytical methods and the determination of emerging pollutants. One of the well-established green extraction techniques is microwave-assisted extraction (MAE). After giving a brief description of MAE principles, the present review comprehensively describes the applications of MAE in the past six years for the determination of the main families of emerging organic pollutants in the environment. Compared to other extraction techniques, MAE offers many advantages, such as great reductions in extraction time and solvent consumption, as well as the possibility of performing multiple extractions, thereby increasing sample throughput. From a technological point of view, most future application areas are likely to focus on improving the flexibility of recently introduced sequential systems with the capacity to control conditions in each extraction vessel.