A novel thin film composite (TFC) membrane featuring a polyamide bilayer was prepared on a porous polysulfone support using sequential interfacial polymerization. A conventional polyamide membrane prepared using m-phenylenediamine (MPD) in water and trimesoyl chloride (TMC) in hexane via interfacial polymerization was subsequently immersed into an alkaline aqueous solution of a hexafluoroalcohol (HFA)-containing aromatic diamine (HFA-MDA) to form an HFA-substituted aromatic polyamide layer (HFAPA) on the surface of the conventional (or reference) polyamide layer (REFPA). Water contact angle (theta(w)) measurements indicated that the surface of the membrane becomes much more hydrophobic (theta(w) 140) after forming the additional HFAPA layer onto REFPA (theta(w) 78) although cross-sectional TEM images showed no significant increment in film thickness. The HFAPA-on-REFPA bilayer membrane, which features a more hydrophobic surface than the conventional REFPA membrane, exhibited improved salt rejection (ca. 50% reduction in salt passage) with a small loss in water flux (ca. 8% reduction) compared to the REFPA membrane, resulting in an excellent combination of salt rejection and water flux. Moreover, higher boron rejection was also achieved using the bilayer membrane (HFAPA-on-REFPA) compared to the REFPA membrane. (C) 2013 Elsevier B.V. All rights reserved.