Integrating ionic liquids (ILs) with polymers in a composite structure enables the creation of intelligent materials that synergistically combine the characteristics of specific polymers and ILs. This work explores the impact of introducing PAN and [EMIM][Ac] separately and their combined incorporation into the PES solution to produce electrospun membranes tailored for efficient oil/water separation. The optimization of the blending process for both the PES/PAN and PES/IL in the spinning solution was carried out. Compared to the pristine PES membrane and by adding hydrophilic PAN (10- 40 v%) to the PES solution, hydrophilicity, pure water flux (PWF) (1265 L/m2h), and oil/water separation efficiency (86%) have been improved while the mechanical properties of the membranes decreased. Incorporating [EMIM][Ac] resulted in a decrease in the fiber diameter, mechanical properties, and PWF (605 L/m2h) along with an increase in the straightness, compactness, roughness, and oil/water separation efficiency (94%). The tricomponent electrospun membrane exhibits superior water permeability (1356.85 L/ m2 h) and oil rejection efficiency (87%) compared to its binary counterparts.