This chapter provides a comprehensive overview on the application of chitosan membranes in pervaporation and permeation processes. Pervaporation is a widely used membrane process for volatile liquid mixture separation. The separation of solvents is of extreme importance in a variety of industries ranging from chemical to food and pharmaceutical. The main thrust of research efforts has been concentrated on the polymeric membranes: investigation of new polymeric materials, modeling of component transport through dense polymers and description of their application. Chitosan membranes, owing to their hydrophilicity, biocompatibility, and ease of modification have been extensively applied for numerous pervaporation processes. The general overview of the preparation and application of different kinds of chitosan membranes e.g. crosslinked, blended, hybrid, grafted and chitosan membranes on porous support, in the separation of various solvents is presented. The progress of research, challenges and opportunities, as well as the prospect of pervaporation technique are also discussed.