The oil and gas industry and related applications generate large quantities of oily wastewater, which can adversely affect the environment and human health if not properly handled. This study aims to prepare polyvinylidene fluoride (PVDF) membranes incorporated with polyvinylpyrrolidone (PVP) additives and utilize them to treat oily wastewater through the ultrafiltration (UF) process. Flat sheet membranes were prepared using PVDF dissolved inN,N-dimethylacetamide, followed by the addition of PVP ranging from 0.5 to 35 g. Characterization by scanning electron microscopy (SEM), water contact angle, Fourier transform infrared spectroscopy (FTIR), and mechanical strength tests were performed on the flat PVDF/PVP membranes to understand and compare the changes in the physical and chemical properties of the membranes. Prior to the UF process, oily wastewater was treated by a coagulation–flocculation process through a jar tester using polyaluminum chloride (PAC) as a coagulant. Based on the characterization of the membrane, the addition of PVP improves the physical and chemical properties of the membrane. The membrane’s pore size becomes larger, which can increase its permeability and flux. In general, the addition of PVP to the PVDF membrane can increase the porosity and decrease the water contact angle, thereby increasing the membrane’s hydrophilicity. With respect to filtration performance, the wastewater flux of the resultant membrane increases with increasing PVP content, but the rejections for TSS, turbidity, TDS, and COD are reduced.