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Existing toxic solvents in the manufacturing of polymeric membranes have been raising concerns due to the risks of exposure to health and the environment. Furthermore, the lower tensile strength of the membrane renders these membranes unable to endure greater pressure during water treatment. To sustain a healthier ecosystem, fabrication of polyvinylidene fluoride (PVDF) hollow fiber membrane using a less toxic solvent, triethyl phosphate (TEP), with a lower molecular weight polyethylene glycol (PEG 400) (0–3 wt.%) additive were experimentally demonstrated via a phase inversion-based spinning technique at various air gap (10, 20 and 30 cm). Membrane with 2 wt.% of PEG 400 exhibited the desired ultrafiltration asymmetric morphology, while 3 wt.% PEG 400 resulting microfiltration. The surface roughness, porosity, and water flux performance increased as the loading of PEG 400 increased. The mechanical properties and contact angle of the fabricated membrane were influenced by the air gap where 20 cm indicate 2.91 MPa and 84.72°, respectively, leading to a stronger tensile and hydrophilicity surface. Lower toxicity TEP as a solvent helped in increasing the tensile properties of the membrane as well as producing an eco-friendly membrane towards creating a sustainable environment. The comprehensive investigation in this study may present a novel composition for the robust structure of polymeric hollow fiber membrane that is suitable in membrane technology. [ABSTRACT FROM AUTHOR]