Theoretical ternary phase diagrams with very good agreement with experimental cloud point data were constructed for water/N,N-dimethyl-acetamide (DMAc)/polyethersulfone (PES) and water/N-methyl-2-pyrrolidone (NMP)/polyethersulfone systems. Theoretical phase diagrams were determined based on the extended Flory-Huggins theory of polymer solutions. To construct the theoretical phase diagrams, all binary interaction parameters were determined accurately and thoroughly revisited. Also, the structures of membranes prepared of these systems by phase separation process were investigated. The morphological studies showed that in spite of better miscibility between water and DMAc compared to water and NMP, channel-like structures were observed in membranes prepared of water/NMP/PES systems but tear-like structures with more spongy areas were observed in membranes prepared of water/DMAc/PES system. According to the constructed theoretical ternary phase diagrams of these systems, these unexpected observations were attributed to the higher concentration of polymer in the polymer-rich phase of water/DMAc/ PES system, which causes an early vitrification in this system which suppresses the growth of macrovoids. (c) 2007 Elsevier Ltd. All rights reserved.