Cellulose triacetate (CTA) membranes for forward osmosis (FO) were fabricated in this study. The fundamental engineering and science of CTA membrane formation were explored by casting the membranes from different solvent systems and characterizing the membranes' morphology using advanced tools such as positron annihilation spectroscopy (PAS). N-Methyl-2-pyrrolidone (NMP) and dioxane were used as the solvents for CTA in the membrane fabrication process. It was found that the choice of solvents for membrane fabrication significantly affects the morphology of as-cast membranes and their FO performance. The CTA membrane cast using NMP as the main solvent has shown poor NaCl rejection but high water flux, whereas the CTA membrane cast using dioxane as the main solvent has excellent NaCl rejection but low water flux. SEM and PAS data reveal that the sublayer of CTA membranes cast from dioxane has a close-cell and much denser structure compared to that cast from NMP. As a result, the former has a significantly lower water flux than the latter in the FO process (5 vs. 27 LMH) using a 2 M NaCl draw solution. Surprisingly, with the addition of acetic acid into the dioxane/acetone solvent system, the resulting membrane has a significantly more porous and open-cell sublayer structure. In addition to the pore forming ability of acetic acid, FTIR spectra confirm the formation of acetic acid/dioxane complexes in the casting solution. Thus, as validated by PAS spectra, the free volume of the active layer of the resultant CTA membranes increases after the addition of acetic acid into the dioxane/acetone casting solution and the water flux increases to 23 LMH using a 2 M NaCl draw solution. Molecular simulations were also conducted to examine CTA polymeric chains in different solvent systems and to witness different CTA chain behaviors in these solvents that leads to significant differences in the as-cast membranes' morphology. (C) 2012 Elsevier B.V. All rights reserved.