In this study, high pervaporation separation performance composite membranes were prepared by casting aqueous chitosan solution on a skin-free cellulose acetate (CA) membrane surface. A series of skin-free CA membrane prepared via immersion precipitation has been successfully fabricated using in-situ casting process with different polymer concentrations upon the non-woven support. The effect of the casting solution concentration on the membrane morphology was characterized by SEM and AFM. Compared with the traditional asymmetric CA membrane, the skin-free CA membranes with a higher water flux were obtained. The influence of CA support layer structure on pervaporation separation performance of the chitosan/CA composite membrane was also studied.