Star-shaped macromolecules with C60 fullerene branching centers were used as modifiers of poly(2.6-dimethyl-1.4-phenylene oxide) matrix to obtain mixed matrix membranes. Two types of star modifiers were synthesized i) six-arms star with six polystyrene arms grafted onto C60 center and ii) twelve-arms hybrid star with six polystyrene arms and six copolymer poly(2-vinylpyridine)-block-poly(tert-butylmethacrylate) arms grafted onto C60 center. The membrane structures were studied by scanning electron microscopy. The transport properties of the membranes were determined by using sorption and pervaporation tests toward methanol and ethylene glycol over a wide concentration range. All membranes showed high affinity for methanol. The separation factor reached its maximum level at 5 wt% modifier concentration in the membrane. Polar hybrid arms were shown to change the membranes’ morphologies and considerably improve their transport properties.