Nanoporous polyethersulfone (PES) membranes were synthesized using lithium perchlorate (LiClO4) as an additive in the casting dope. Membranes were prepared through phase inversion method from PES/polyethylene glycol (PEG)/LiClO4 system using dimethylformamide (DMF) as the primary solvent and water as secondary solvent. Effect of LiClO4 on the membrane performance was studied by varying its composition from 0 wt% to 5 wt%. SEM studies indicated that the LiClO4 blended PES membranes possessed dense top surface and finger-like sub-layer. Atomic force microscopy analysis clearly showed that the addition of LiClO4 resulted in nano-structure membranes with small surface pore size and low surface roughness. Contact angle measurements confirmed the enhanced hydrophilicity of the composite membranes due to LiClO4 inclusion. Pure water flux measurements demonstrated high flux capabilities of LiClO4 blended PES membranes as compared with pristine PES membrane. Dye rejection performance studies using Congo red, Crystal violet and Methylene blue as probe molecules, indicated a better dye removal efficiency of the LiClO4 incorporated PES membrane. Fouling analysis in terms of fouling recovery ratio exhibited the better anti-fouling ability of the PES membranes due to LiClO4 incorporation. Analysis on the obtained result showed that the 3 wt% LiClO4 blended PES membrane possessed desirable characteristics among the synthesized PES/PEG/LiClO4 membrane series. © 2018 Desalination Publications. All rights reserved.