Polyvinylidene fluoride (PVDF) hollow fiber ultrafiltration membranes consisted of TiO2 and different molecular weight (M-w) of polyvinylpyrrolidone (PVP) (i.e., 10, 24, 40, and 360 kDa) were prepared to treat synthesized oily wastewater. The membrane performances were characterized in terms of pure water flux, permeate flux, and oil rejection while their morphological properties were studied using SEM, AFM, and tensile tester. Results show that the PVDF-TiO2 composite membrane prepared from PVP40k was the best performing membrane owing to its promising water flux (72.2 L/m(2).h) coupled with good rejection of oil (94%) when tested with 250 ppm oily solution under submerged condition. It is also found that with increasing PVP M-w, the membrane tended to exhibit higher PVP and protein rejection, greater mechanical strength, smaller porosity, and a smoother surface layer. Regarding the effect of pH, the permeate flux of the PVDF-PVP40k membrane was reported to increase with increasing pH from 4 to 7, followed by decrease when the pH was further increased to 10. Increasing oil concentration in the feed solution was reported to negatively affect the water flux of PVDF-PVP40k membrane, owing to the formation of thicker oil layer on the membrane surface which increased water transport resistance. A simple backflushing process on the other hand could retrieve approximately 60% of the membrane original flux without affecting the oil separation efficiency. Based on the findings, the PVDF-TiO2 membrane prepared from PVP40k can be potentially considered for oily wastewater treatment process due to its good combination of permeability and selectivity and reasonably high water recovery rate.