The oily wastewater produced by a variety of industrial operations presents a serious threat to both humans and the environment. Separation efficiency, good mechanical stability, high flux, and recyclability are critical parameters for a suitable oil-water separation membrane. In this study, a novel blend membrane of (poly (lactic acid)/poly (butylene adipate-co-terephthalate)) with hesperidin-NPs was synthesized by using the phase inversion technique to effectively separate oily-water emulsions. Herein, hesperidin (HSP) was harnessed for the first time as a green agent to optimize its content in the polymeric matrix. (FTIR) Fourier transform infrared spectroscopy, (FESEM) Field emission scanning electron microscopy, (CA) contact angle, mechanical tester, pore size and porosity were utilized to comprehensively characterize the manufactured (PLA/PBAT/HSP) membranes. The current work presents the proposed interaction mechanism between the contents of PLA/PBAT/HSP and the interaction mechanism of PLA/PBAT/HSP membrane with H2O molecules. The synthesized (PLA/PBAT/HSP) membrane manifested high wettability and has a 49° water contact angle and oleophobicity under a water contact angle of 146±2° for diesel oil. The PLA/PBAT membrane exhibited a homogeneous and symmetric spongy-like structure from top to bottom across its entire cross-section with very tiny active layer observed at the top surface of the membrane in FESEM images. Meanwhile, incorporating of 0.0125wt.% HSP into the casting solution has resulted in a significant change in the structural morphology. Furthermore, upon adding the HSP to the polymeric matrix, distinct changes in the structure were formed, which resulted in enhancing the mechanical features (tensile strength) of the membranes. Modified membrane with 0.025wt.% HSP displayed an optimal flux for pure water (220.5L/m2.h1) and the modified membranes maintained a high rejection (more than 99%) against oil-water emulsions. Outcomes demonstrated that the improved permeation and separation characteristics of the (PLA/PBAT/HSP) membranes could present a potential option to treat applications that use oily wastewater.