Hollow fiber membranes were prepared from polyethersulfone/additives/NMP&DMSO system via phase inversion induced by precipitation in non-solvent coagulation bath. The interaction effects of polyethylene-glycol (PEG), propionic-acid (PA), Tween-20, PEG molecular weight and polyvinyl-pyrrolidone (PVP) on morphology and performance of synthesized membranes were investigated. Taguchi method (L16 orthogonal array) was used initially to plan a minimum number of experiments. 32 membranes were synthesized (with two replications) and their permeation flux and TOC rejection properties to oily wastewater treatment were studied. The obtained results indicated that addition of PA to spinning dope decreases flux while it increases TOC rejection of prepared membranes. Also, the result shows that addition of PVP, Tween-20 and PEG content in spinning dope enhances permeation flux while reducing TOC rejection. The obtained results indicated that the synthesized membranes was effective and suitable for treatment of the oily wastewater to achieve up to 92.6, 98.2, and 98.5% removal of TOC, TSS, and OGC, respectively with a flux of 247.19 L/(m2h). Moreover, Hermia’s models were used for permeation flux decline prediction. Experimental data and models predictions were compared. The results showed that there is reasonable agreement between experimental data and the cake layer model followed by the intermediate blocking model.