The article focuses on multicomponent system separation with the use of an innovative membrane-based technique i.e. pervaporation. Pervaporation is a membrane technique for separation of liquid mixtures on solid nonporous membranes. Pervaporation is used in this study to separate a quaternary system acetone-butanol-ethanol-water. Such a system may be derived from ABE fermentation process, and the resulting product, biobutanol, is a potential biofuel and may be used in internal combustion engines.Experiments in the study involving concentration of butanol by pervaporation were performed using PERVAP 4060 flat-sheet commercial membrane. To describe the PV process a semi-empirical approach was used. As a result of experiments and calculations permeance coefficients were obtained. Separation and permeance factors were calculated to assess the efficiency of the system separation. Beforehand, activity coefficients were determined for all the components of the mixture with the NRTL equation. Separation coefficients for all the components differed depending on process parameters: concentration, feed flow rate and process temperature. The study confirmed the separation effect of the quaternary system. The most interesting results were obtained for the concentration of butanol. Pervaporation allows to concentrate butanol over 10 times. The permeance coefficient reached for butanol an average value of 7.06·10-3 in comparison with the results for ethanol 3.24·10-2 and acetone 1.83·10-2 [kmol(m2h)-1]. The temperature change from 50 to 70°C led to an increased permeance factor and there was no apparent effect on it in the feed flow rate. Due to the hydrophobicity of the membrane water fluxes in the quaternary system were negative.