This study focuses on the synthesis and characterization of dual-layer sulfonated polyphenylenesulfone (SPPSu) nanocomposite hollow fiber nanofiltration membranes incorporating titanium dioxide (TiO2) nanoparticles through the phase inversion technique. Advanced tools and methods were employed to systematically evaluate the properties and performance of the newly developed membranes. The investigation primarily centered on the impact of TiO2 addition in the SPPSu inner layer on pure water permeability and salt rejection. The nanocomposite membranes exhibited a remarkable three-fold increase in pure water permeability, achieving a flux of 5.4 L/m2h.bar compared to pristine membranes. The addition of TiO2 also enhanced the mechanical properties, with an expected tensile strength increase from 2.4 to 3.9 MPa. An evaluation of salt rejection performance using a laboratory-scale filtration setup revealed a maximal rejection of 95% for Mg2SO4, indicating the effective separation capabilities of the modified dual-layer hollow fiber nanocomposite membranes for divalent ions. The successful synthesis and characterization of these membranes highlight their potential for nanofiltration processes, specifically in selectively separating divalent ions from aqueous solutions, owing to their improved pure water flux, mechanical strength, and salt rejection performance.