Pervaporation (PV) is an effective approach for the removal of trace or micro substances from solutions. PV membrane is considered to be the most essential element for this process. In this study, the fabrication of ceramic hollow fiber PV membranes is demonstrated through multilayer assembly of poly(4-styrenesulfonic acid) and chitosan. The surface and cross-section morphologies, physical and chemical structures as well as the hydrophilicity of the membranes were characterized by field emission scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectrophotometer (FTIR) and water contact angle, respectively. The PV performance of the composite membranes was investigated by dehydration of water-ethanol solution. The effect of assembly solution concentration on PV performance was studied systematically. The assembled composite membranes with the concentration of 0.75 wt% PSS solution exhibited the highest PV separation index (PSI) value of 4.47 x 10(5) with flux of 495 g/m(2) h and separation factor of 904 for dehydration of 10 wt% water-ethanol solution at 70 degrees C.