A novel poly(amide-urethane@imide) reverse osmosis (RO) composite membrane with chlorine-tolerant property was prepared on a polysulfone supporting film through two-step interfacial polymerization. The crosslinking agent - 5-choroformyloxyisophaloyl chloride (CFIC) was first waded with 4-methyl-phenylenediamine (MMPD) via interfacial polymerization to get the nascent poly(amide-urethane) base membrane (CFIC-MMPD) without curing treatment. Then the resultant base membrane contacted again with the second aqueous solution containing functional secondary amine - N,N'-dimethyl-m-phenyle-nediamine (DMMPD) to obtain the poly(amide-urethane@imide) TFC RO membrane (MMPD-CFIC@CFIC-DMMPD). X-ray photoelectronic spectroscopy (XPS) was combined with attenuated total reflectance infrared (ATR-IR) to verify that the ultrathin polyimide film (CFIC-DMMPD) has been successfully grafted on the surface of the MMPD-CFIC base membrane. The images of scanning electronic microscopy (SEM) and atomic force microscope (AFM) showed that the poly(amide-urethane@imide) membrane has much smoother, more hydrophilic surface than the poly(amide/imide-urethane) membrane (MMPD/DMMPD-CFIC) prepared by conventional one-step interfacial polymerization of CFIC and composite MMPD/DMMPD. However, the permeation experiment revealed that the poly(amide-urethane@imide) membrane has a slight loss in both salt rejection and water flux than the poly(amide/imide-urethane) membrane and conventional commercialized polyamide membrane (MPD-TMC), but exhibits better chlorine-tolerant property clue to the introduction of ultrathin polyimide film (CFIC-DMMPD) on the outmost surface of the TFC RO membrane, and the combination of IR and XPS analyses shows a good agreement with the chlorine exposure results of membranes. (C) 2014 Elsevier B.V. All rights reserved,