The design and engineering of membrane structure that produces low salt leakage and minimized internal concentration polarization (ICP) in forward osmosis (FO) processes have been explored in this work. The fundamentals of phase inversion of cellulose acetate (CA) regarding the formation of an ultra-thin selective layer at the bottom interface of polymer and casting substrate were investigated by using substrates with different hydrophilicity. An in-depth understanding of membrane structure and pore size distribution has been elucidated with field emission scanning electronic microscopy (FESEM) and positron annihilation spectroscopy (PAS). A double dense-layer structure is formed when glass plate is used as the casting substrate and water as the coagulant. The thickness of the ultra-thin bottom layer resulted from hydrophilic-hydrophilic interaction is identified to be around 95 nm, while a fully porous, open-cell structure is formed in the middle support layer due to spinodal decomposition. Consequently, the membrane shows low salt leakage with mitigated ICP in the FO process for seawater desalination. The structural parameter (S(t)) of the membrane is analyzed by modeling water flux using the theory that considers both external concentration polarization (ECP) and ICP, and the S(t) value of the double dense-layer membrane is much smaller than those reported in literatures. Furthermore, the effects of an intermediate immersion into a solvent/water mixed bath prior to complete immersion in water on membrane formation have been studied. The resultant membranes may have a single dense layer with an even lower S(t) value. A comparison of fouling behavior in a simple FO-membrane bioreactor (MBR) system is evaluated for these two types of membranes. The double dense-layer membrane shows a less fouling propensity. This study may help pave the way to improve the membrane design for new-generation FO membranes. (C) 2010 Elsevier B.V. All rights reserved.