Pervaporation is an important alternative membrane separation process compared to the distillation technique, and a relatively high separation factor is required to lower the energy demand. Solution processable nanocomposite membranes prepared by incorporating functionalized graphene sheets (FGS) loaded in various concentrations into the chitosan matrix have been employed for the pervaporative dehydration of ethanol and isopropanol. Incorporation of FGS leads to an increase of surface hydrophilicity of the chitosan membranes along with an increase in membrane tortuosity that was favorable to the selective permeation of water molecules. The nanocomposite membrane containing 2.5 wt % FGS gave the highest selectivities of 7781 and 1093 for isopropanol-water and ethanol-water mixtures, respectively, when tested for 10 wt 96 water-containing feed mixture. Membranes were characterized by wide-angle XRD, SEM, contact angle, and optical profilometry techniques. The Flory-Huggins theory was employed to estimate the polymer-solvent interaction parameter. Diffusion values and Arrhenius activation energy parameters provided quantitative evidence for the observed increase in water selectivity at higher loading of FGS.