In this work, membranes from poly (2,6-dimethyl-1,4-phenylene oxide) composites containing a new type of modifier based on zinc chloride and acetamide in a molar ratio of 1 : 3, which belongs to a class of deep eutectic solvents, were developed for acetic acid dehydration by pervaporation. The membrane structure was investigated by scanning electron microscopy and X-ray diffraction analysis; thermal stability was determined by thermogravimetric analysis. The transport properties were studied by means of vacuum pervaporation in separation of water – acetic acid mixture. It was shown that the introduction of deep eutectic solvent leads to an increase in membrane total flux and also an increase in selectivity at small amounts of the modifier. The highest separation factor was reached by a membrane containing 5 wt % modifier (more than 99 wt % water in permeate).