Microporous polyethylene (PE) membranes having a controlled pore size were produced via the thermally induced phase separation process by manipulation of the phase boundary of the PE/diluent blend and process conditions. The phase boundary of the PE blend, caused by upper critical solution temperature type phase behavior, was controlled by the use of a diluent mixture, that is, an isoparaffin/soybean oil mixture. The phase-separation temperature of the PE/soybean oil blend was always higher than that of the PE/isoparaffin blend. In PE /(isoparaffin /soybean oil) ternary blends, the phase-separation temperature of the ternary blend rapidly increased with increasing soybean oil content in the diluent mixture. Furthermore, the phase-separation temperatures of ternary blends were always higher than that of the PF/soybean oil blend, regardless of the blend compositions, when the diluent mixture contained more than 50 wt % soybean oil. The observed phase behavior of the ternary blends was analyzed with interaction energy densities calculated with the Flory-Huggins theory and ternary stability conditions. The growth of droplets caused by both coalescence and the Oswald ripening process was observed after the onset of phase separation. As the blends became less stable, the droplet growth rate increased, and larger equilibrium droplets were formed. Microporous membranes with the desired pore structure could be prepared by control of the phase boundary and the variation of processing conditions such as the quenching depth, annealing time, and cooling rate. (C) 2008 Wiley Periodicals, Inc.