Hyperbranched polyethyleneimine functionalized silica (PEI-SiO2) nanoparticles with considerable hydrophilicity were synthesized and incorporated into a polysulfone (PSF)/dimethylacetamide (DMA)/polyvinylpyrrolidone (PVP) membrane casting solution in five different ratios to fabricate PEI-SiO2/PSF nanocomposite membranes using nonsolvent-induced phase separation. The hydrophilic PEI-SiO2 nanoparticles were characterized by TEM, FTIR, TGA, and XPS analyses. Morphology, water contact angles, mean pore sizes, overall porosity, tensile strengths, water flux, antifouling and the dye separation performances of the PEI-SiO2/PSF membranes were also studied. The PEI-SiO2 nanoparticles were uniformly dispersed in the PSF-based membranes, where a fall in the water contact angle was observed from 65.4° to 49.7° by addition of 2 wt% nanoparticles. The fouling resistance parameters of the PEI-SiO2/PSF membranes were declined with an increase in the nanoparticle concentration, suggesting the superior hydrophilic nature of the PEI-SiO2 nanoparticles. The permeability of the nanocomposite membranes was increased from 38.5 to 70 L m−2 h−1 bar−1 by incorporation of 2 wt% PEI-SiO2. Finally, improvements were observed in the flux recovery ratio (95.8%), Reactive Green 19 dye rejection (99.6%) and tensile strengths of the PEI-SiO2/PSF membranes over the neat PSF and SiO2/PSF membranes, which were used as controls. The results of this study demonstrate the promising application of PEI-SiO2 nanoparticles in improving the separation and antifouling performances of the PSF membranes for water purification.