Since several decades ago, the application of pervaporation (PV) technology has been mainly aimed at the separation of different types of water-organic, organic-water and organic-organic mixtures, reaching its large-scale application in industry for the dehydration of organics. Today, the versatility and high selectivity toward specific compounds have led its consideration to other types of application such as the assisted chemical and bio-chemical reactions. The focus of this review is to provide a compelling overview on the recent developments of PV combined with chemical and bio-chemical reactions. After a general introduction of PV and its theoretical background, particular emphasis is given to the results obtained in the field for different reactions considered, identifying the key features and weak points of PV in such particular applications. Furthermore, future trends and perspectives are also addressed according to the latest literature reports.