Microporous poly (ethylene-co-vinyl alcohol) (EVAL) membranes can be prepared by the solution casting method in combination of thermally induced phase separation (TIPS) with solvent evaporation. A cosolvent of isopropanol and water (3:2 w/w) is used to prepare the casting solution. EVAL membranes of different bulk or true densities, porosity, flexibility, crystallinity, and structure can be obtained by adjusting the casting temperature. A pseudo-binary temperature-concentration phase diagram of the EVAL-cosolvent system has been proposed, based on the information obtained from SEM, DSC, and light transmittance studies, to account for the membrane formation mechanism. The dense membranes were obtained when the casting temperature was higher than the upper critical solution temperature (UCST) of the system, but they might contain some nonSEM-observable micropores if the casting temperature was below the glass transition temperature (T-g) of EVAL. The porous and the least crystalline membranes with a honeycomb-like morphology were obtained through liquid-liquid demixing and vitrification at a casting temperature between the UCST and the dynamic crystallization temperature (T-c). Highly porous and crystalline membranes were obtained when they were prepared at temperatures near T-c. In this case, the particulate membranes were resulted from solid-liquid demixing mainly via TIPS, and membranes with leafy morphology were created through liquid-liquid demixing and then followed with immediately crystallization.