Abstract: Polyether block amide/polyacrylonitrile (PEBAX/PAN) and nano-fumed silica filled PEBAX/PAN composite membranes were prepared for pyridine separation via pervaporation. The membranes were characterized by SEM, XRD and FT-IR, and the results indicate that n-SiO₂ is physically blended with polymer. Swelling property and pervaporation performance were explored using model gasoline composed of pyridine and n-heptane. Swelling results show that the degree of swelling in model gasoline (pyridine and n-heptane) increases with pyridine concentration and temperature. The membrane with 10‰(wt) nano-fumed silica exhibits better total permeation flux, while the membrane with 5‰(wt) nano fumed silica shows better separation factor. Both total permeation flux and separation factor increase with the increase of pyridine concentration in the feed, while feed temperature increase enhances permeation flux but weakens separation factor. When the pyridine concentration is 5000 μg·g^-1 at 30℃, the total permeation flux and separation factor of the membrane with 5‰(wt) nano-fumed silica are 5.05 kg·m^-2·h^-1 and 3.39, respectively. The results indicate that the silica filled PEBAX/PAN membrane is efficient in pyridine enrichment.