The problem of n-butanol ‒ water separation arises from the widespread interest to the search for alternative energy sources. To solve the problem by membrane technique, pervaporation membranes were developed on the basis of polyphenyleneisophthalamide modified with hybrid star macromolecules containing six arms of polystyrene and six arms of poly-tert-butyl methacrylate on the fullerene (C60) core. The structure was studied by scanning electron microscopy that reveal a tendency to form domains in the membranes modified by star macromolecules. Modification of the membrane by star fullerene (C60)-containing macromolecules led to a sharp increase in the selectivity and permeability of the membrane. Transport properties of novel membranes were studied in pervaporation of n-butanol‒water mixtures to separate n-butanol from water admixture for further use of this alcohol as industrial solvent and biofuel. It was found that introduction up to 5 wt% star modifier increases the separation efficiency of membranes in dehydration of n-butanol (water content in the permeate reaches 99.9 wt% while pervaporation separation index comes up to 400 kg/m2h), which allows obtaining high-purity n-butanol.