Pervaporation (PV), a membrane-based separation technique, has become an emerging technological tool in separating liquids during the last few decades. It has gained rapid interest because of its environmentally benign nature, highly energy efficient process and availability of various types of new tailor-made membranes for all types of PV separating applications. The dehydration of organic solvents has been widely studied by PV because the availability of high-purity solvents has been a major concern for many industrial applications. In this regard, many membrane materials such as polymers, copolymers, blends, cross-linked polymers, zeolites, various salts were studied extensively. Among various types, polymer-based membranes have become more attractive because of structure of the polymer matrices can be altered easily and also less expensive. During the past decade, among the various polymers, carbohydrate polymers, viz., sodium alginate, chitosan, celluloses, etc., have been studied extensively. The use of these polymers provides better mechanically stable membranes with better hydrophilicity. Further, nanocomposite membranes of carbohydrate polymer emerged by incorporating various metal or metal oxides like TiO2, ZnO, silver, zeolites, clay, graphene, etc. in polymer matrices, which makes membranes highly selective and improves overall PV separation characteristics. In this chapter, the carbohydrate polymer membrane-based pervaporation process will be highlighted in detail, the progress of the developments in PV technology and how various carbohydrate polymer based membranes progressed and their overall performance in effective dehydration of solvents will be discussed.