Development of asymmetric channel morphology driven by coagulation-induced phase separation of genistein (G) modified poly(ether sulfone)/poly(vinyl pyrrolidone) (PES/PVP) blends has been examined in relation to their miscibility phase diagram. PES/G pairs turned out to be miscible in the amorphous state, whereas solid–liquid phase separation occurred at high genistein compositions. The solid–liquid phase diagram involving the liquidus and solidus lines were computed self-consistently in the framework of the combined free energy of Flory-Huggins for liquid–liquid phase separation and phase field free energy for crystal solidification. The ternary phase diagram of PES/PVP/G blends was subsequently established that consisted of various coexistence regions. The actual amounts of genistein incorporated in the PES/PVP membranes were determined as a function of weight percent of genistein in feed. On the basis of UV-vis spectroscopy, the extent of genistein leaching during incubation in human blood was evaluated in conjunction with the PVP leaching from the blend membrane.