In this study permeation and separation characteristics of dimethylformamide (DMF)/water mixtures were investigated by pervaporation (PV), vapor permeation (VP), and vapor permeation with temperature difference (TDVP) methods using alginate membranes crosslinked with calcium chloride. The effects of membrane thickness (30-90 mu m), feed composition (0-100 wt%), operating temperature (30-50 degrees C) on the permeation rates and separation factors were investigated. The permeation rate was found to be inversely proportional to the membrane thickness whereas separation factor increased as the membrane thickness was increased. It was observed that the permeation rates in VP and TDVP were lower than in PV however the highest separation factors were obtained with TDVP method. Alginate membranes gave permeation rates of 0.97-1.2 kg/m 2 h and separation factors of 17-63 depending on the operation conditions and the method. In addition, sorption-diffusion properties of the alginate membranes were investigated at the operating temperature and the feed composition. It was found that the sorption selectivity was dominant factor for the separating of DMF/water mixtures.