Layer-by-layer assembly is a versatile technique for fabricating nanofiltration membranes, where multiple layers of polyelectrolytes are usually required to achieve reasonable separation performance. In this work, an ionic strength directed self-assembly procedure is described for the preparation of nanofiltration membranes consisting of only a single bilayer of poly(diallyldimethylammoniumchloride) and poly(sodium-4-styrenesulfoate). The influence of background ionic strength as well as membrane substrate properties on the formation of single-bilayer membranes are systematically evaluated. Such a simplified polyelectrolyte deposition procedure results in membranes having outstanding separation performance with permeating flux of 14.2 ± 1.5 L∙m^–2∙h^–1∙bar^–1 and Na₂SO₄ rejection of 97.1% ± 0.8% under a low applied pressure of 1 bar. These results surpass the ones for conventional multilayered polyelectrolyte membranes. This work encompasses an investigation of ionic strength induced coiling of the polyelectrolyte chains and emphasizes the interplay between-polyelectrolyte chain configuration and substrate pore profile. It thus introduces a new concept on the control of membrane fabrication process toward high performance nanofiltration.