In this current study, poly (methyl vinyl ether maleic anhydride) (PMVEAMA), a sustainable additive, was incorporated into poly (ether-ether sulfone) (PEES) polymer to design a novel polymeric hybrid membrane for the efficient filtration of toxic pentachlorophenol (PCP) from an aqueous medium. Hydrophilic additives significantly altered the membrane's morphology, structure, porosity, water content, and flux performance compared to the bare PEES membrane. The influence of PMVEAMA on the structural modification of the synthesized polymer membrane was confirmed by SEM, ATR-FTIR, XRD, AFM, zeta potential and contact angle. Findings revealed that the addition of PMVEAMA to the PEES polymer enhances the porosity (17.7%–28.9%), water content (29.8%–39.8%), and pure water flux (186 Lm−2h−1 to 349 Lm−2h−1). The effect of PMVEAMA concentration on the PEES membrane exhibited more finger like pores, better porosity and hydrophilicity, reduced surface roughness, fouling and increased permeability. The fouling studies exhibit an improved 57% PCP rejection and permeation flux of 22.3 Lm−2h−1 due to the addition of the hydrophilic additive. Surprisingly, the incorporation of PMVEAMA into the bare PEES membrane resulted in a high flux recovery ratio of 73.7%. The antifouling properties and enhanced permeability of the PEES/PMVEAMA membrane indicates its potential application in water purification sectors for the efficient separation of contaminants.