A polycarbonate (PC)/(DMF/metal salt) complex membrane was utilized in the pervaporation of alcohol/water mixtures. The effects of the presence of metal salt in the casting solution, the polycarbonate concentration, and the kinds of coagulation media on the formation of membranes were studied. In addition, the effects of feed composition, size of the alcohol, and the degree of swelling on the pervaporation performances were investigated. Compared with the membrane without additive, the PC/(DMF/metal salt) complex membrane shows an improvement in the pervaporation separation index (PSI).