Phase separation of poly(vinylidene fluoride) dimethylformamide solution was induced by the penetration of water vapor, and the porous membrane was formed. As the humidity in the gas phase increased, membrane morphology changed in the order of dense, porous (cellular), and lacy-like structures. At the higher humidity condition, spherical bead structure was observed, which is likely to be crystalline spherulite. With the increase of the initial polymer concentration, less pores were formed in the case of the lower humidity of 20%, whereas more distinguished spherical structures were formed in the case of higher humidity of 40%. The obtained membrane morphologies were discussed based on both the calculated composition paths during the process and the phase diagram.