In this study, polyvinylchloride (PVC) membranes were prepared through the immersion precipitation method using a mixture of two solvents (tetrahydrofuran (THF) and dimethyl formamide (DMF)), which had different affinities with the nonsolvent (water). Membranes prepared from PVC/THF/water system showed a sponge-like structure with isolated pores, which were impermeable to water even at a feed pressure of 20 bars, whereas those prepared from PVC/DMF/water exhibited a porous macrovoid containing morphology with a high water flux. The precipitation time and polymer concentration profiles were calculated by using a simple mathematical model and were in good agreement with the experimental findings on PVC/THF/water and PVC/DMF/water systems. By using a mixture of DMF and THF as solvent and changing the mixed solvent composition, membranes with different morphologies from sponge-like to macrovoid containing were obtained. The membranes showed no water flux below a DMF concentration of 50 wt % and then became increasingly permeable with increasing DMF content in the casting solution. Measurement of the system cloud points showed a linear change of system thermodynamics with variation of the mixed solvent composition. The obtained results showed that although the system thermodynamics could explain the overall behavior of the system, but the local changes such as change of membrane performance from impermeable to permeable at a certain mixed solvent composition could not be explained by the thermodynamics alone. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40206.