Dehydration of widely used organic solvents such as acetic acid (AA) and isobutanol (IB) is challenging tasks, which form close boiling mixtures with water. Sodium alginate (SA) thin film composite membranes were prepared and crosslinked with 2,4-toluene diisocyanate (TDI) and glutaraldehyde for dehydration of IB and AA/water mixtures through pervaporation (PV). The crosslinked and uncrosslinked SA composite membranes were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, and universal testing machine for intermolecular interactions, crystalline nature, thermal stability, surface morphology, and tensile strength, respectively. At a feed composition of 98 wt % IB and 95 wt % AA aqueous solutions, the TDI crosslinked SA composite membrane exhibited separation factors of 3229 and 708 with reasonable fluxes of 0.021 and 0.012 kg m−2 h−1, respectively. The results obtained in the study for IB and AA systems were compared with other SA membranes reported in the literature. The membranes appeared to have potential for commercial PV ability to dehydrate the solvents up to desirable purity levels (>99%) and feasibility of preparing them in a composite form which would enable scale-up into modular configurations. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40018.