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A porous substrate plays an important role in constructing a thin-film composite forward osmosis (TFC-FO) membrane. To date, the morphology and performance of TFC-FO membranes are greatly limited by porous substrates, which are commonly fabricated by non-solvent induced phase separation (NIPS) or thermally induced phase separation (TIPS) processes. Herein, a novel TFC-FO membrane has been successfully fabricated by using cellulose triacetate (CTA) porous substrates, which are prepared using a nonsolvent-thermally induced phase separation (N-TIPS) process. The pore structure, permeability, and mechanical properties of CTA porous substrate are carefully investigated via N-TIPS process (CTAN-TIPS). As compared with those via NIPS and TIPS processes, the CTAN-TIPS substrate shows a smooth surface and a cross section combining interconnected pores and finger-like macropores, resulting in the largest water flux and best mechanical property. After interfacial polymerization, the obtained TFC-FO membranes are characterized in terms of their morphology and intrinsic transport properties. It is found that the TFC-FO membrane supported by CTAN-TIPS substrate presents a thin polyamide film full of nodular and worm-like structure, which endows the FO membrane with high water permeability and selectivity. Moreover, the TFC-FO membrane supported by CTAN-TIPS substrate displays a low internal concentration polarization effect. This work proposes a new insight into preparing TFC-FO membrane with good overall performance.