Loose nanofiltration (LNF) is increasingly considered as the powerful technique for dye desalination due to its clear advantages at energy efficiency, selectivity and low pollution. But the membrane materials for loose nanofiltration process still suffer from the low permeance, unsatisfactory selectivity, membrane fouling and high cost. Herein, we propose a new three-step route to fabricate efficient poly(ether sulfone) (PES) LNF membrane, which starts from PES powder modification via mutual radiation-induced grafting polymerization and ensues immersion precipitation phase inversion and amination processes. The obtained PES-based LNF membrane possessed a thinner skin layer and an unusual irregular vesicular pore structure in sublayer instead of the finger-like macrovoids of conventional PES membrane. Thus, it achieved larger filtration permeance (35.5 L m–2 h−1 bar−1), high dye rejection (93.7 % to Congo Red) but low salt rejection (2.9 % to NaCl) during the filtration process of Congo red-containing saline water. It also showed excellent separation stability at high operation pressure and tolerance to acidic, alkaline and chlorine-oxidative conditions. Therefore, such a three-step strategy could endow the PES membrane with both loose and thinner skin layer in a reliable and scalable way, enlightening the development of high-performance LNF membrane for wastewater treatment and resource recovery.