Poly(vinyl alcohol)/polyacrylonitrile blend membranes were prepared to separate pyridine/water mixtures by pervaporation. The membranes were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The effects of membrane composition, feed pyridine concentration, operating temperature, downstream pressure and ultrasound irradiation on the separation process were evaluated. The experimental results indicated that with increasing PVA mass ratio and operating temperature the permeate flux increased but the separation factor decreased, while with increasing feed concentration and downstream pressure the separation factor increased and the permeate flux decreased. It was observed that Ultrasound irradiation enhanced the permeate flux.