Novel mixed-matrix membranes based on polyvinyl alcohol and its composites with carboxyfullerene were developed. Carboxyfullerene was simultaneously used as a modifier and a cross-linker for polyvinyl alcohol. The structural properties of the developed composites were studied by nuclear magnetic resonance, X-ray diffraction analysis, scanning electron microscopy, and sorption experiments. Thermal properties and stability were investigated by thermogravimetric analysis and differential scanning calorimetry. Surface features were studied by measuring the contact angles by water. The transport properties of the developed membranes were studied in ethanol-water mixtures separation by pervaporation (4.4-90 wt.% water in the feed) at different temperatures (22, 35, 50 °C). All membranes were selective with respect to water. The optimal transport properties were obtained for the PVA-carboxyfullerene (3.5 wt.%) membranes containing catalyst p-toluenesulfonic acid.