Membranes were prepared from a casting solution of a water-soluble polymer, poly (vinyl pyrrolidone) (PVP), and a membrane forming polymer, poly(ether sulfone), in 1-methyl-2-pyrrolidone (NMP) as solvent by immersing them in mixtures of water and NMP. It was found that the addition of PVP to the ternary system suppresses the formation of macrovoids in the sub-layer, while the ultrafiltration-type top-layer consists of a closely packed layer of nodules. Using a model for mass transfer in this quaternary system, it is possible to explain the effects of the additive on macrovoid formation. Strong indications are found that the appearance of a nodular structure in the top-layer follows a mechanism of spinodal decomposition during the very early stages of the immersion step.