In the present work transport properties of novel polymer materials were studied in separation of quaternary mixture (n-propanol–acetic acid–propyl acetate–water) and binary mixture (water–acetic acid) by pervaporation that can be used in hybrid process “reaction + pervaporation” to optimize of the propyl acetate production. Physical methods are successfully used to modernize properties of polymer materials without changing the chemical structure of macromolecules. Poly(phenylene oxide) membrane was modified by novel star shaped macromolecules with fullerene С ₆₀ core and arms of different nature. They are twelve-arm star consisted of six nonpolar arms of polystyrene and six polar arms of poly-2-vinylpyridine that are covalently bonded to C ₆₀ core. The membrane structure and thermal stability were studied by SEM, DSC, and TGA. To characterize physical properties, density and contact angles were determined. Membranes modified with the star macromolecules exhibit selectivity to water. The growth of modifier content up to 5 wt% leads to increase of the membrane performance and selectivity, which provides shifting the esterification reaction equilibrium and increasing the ester yield.