Crystalline PVDF was precipitated, respectively, from water/DMF and 1-octanol/DMF solutions to produce membranes with asymmetric and uniform morphologies. The formation mechanisms of these specific structures were described both in the aspects of thermodynamics (equilibrium phase behavior) and the kinetics (diffusion trajectory). The phase diagrams of the investigated systems indicated the possibility of liquid-liquid demixing or crystallization or both during the immersion-precipitation process. The sequence of these phase separation events, which determined the ultimate membrane structure, was attributed to the kinetic factors. Into this context, a quantitative model describing the immersion-precipitation process was considered. The calculated diffusion trajectory and concentration distribution in the nascent membrane were found to be consistent with the experimental membrane morphologies. Moreover, the precipitation rate of the PVDF solution in water and l-octanol were examined by the light transmission experiments. The latter results further confirmed the validity of the mass transfer calculations.