This paper continues research on the physicochemical features of nanocomposites of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and fullerene C-60 with the purpose of using them as a selective layer of composite membranes in pervaporation coupling esterification of acetic acid with ethanol to produce ethyl acetate. The C-60 PPO/MFFC composite membranes containing up to 3 wt%C-60 were prepared in this work. SEM was employed in visualizing the internal morphology of the membranes. The nature of the interaction between PPO and C-60 molecules in composite was studied by NMR. TG analysis reveals the fact of increasing thermal destruction point of the membrane due to certain structural changes of the PPO matrix upon incorporation of the C-60 molecules. Transport properties of composite membranes with a selective layer containing up to 3 wt%Co were studied in the pervaporation of the quaternary mixture: ethanol, acetic acid, ethyl acetate, and water in order to identify the availability of their use in the hybrid process "esterification + pervaporation". The strong permeability enhancement due to the introduction of C-60 particles in the PPO network was observed whereas the selectivity was almost steady. The best complex of transport properties was obtained from the 2%C-60-PPO/MFFC membrane. (C) 2014 Elsevier B.V. All rights reserved.