AbstractTo separate the oil/water mixtures, polyvinylidene fluoride (PVDF) nanofiber mats were produced using electrospinning. Additionally, PVDF films were made using the solvent evaporation method, and the effectiveness of their separation was evaluated against that of nanofiber mats. By choosing oxygen‐functionalized graphene (with HNO3) as a nano reinforcement, the hydrophobic properties of the PVDF materials made using both techniques were transformed into hydrophilic ones. It has been determined how the characteristics of the solution (viscosity, conductivity, molecular weight, surface tension, and contact angle) relate to the diameter of the nanofiber. Fourier transform infrared spectroscopy‐attenuated total reflection (FT‐IR/ATR), x‐rays diffraction (XRD), scanning electron microscope, thermogravimetric analyses (TGA)/DTG, and differential scanning calorimetric (DSC) have been used to study the chemical and crystal structures, morphology, and thermal behavior of PVDF materials. The addition of oxygen‐functionalized graphene was found to cause a peak in the PVDF composites' FT‐IR/ATR spectrum, roughly in the wavenumber 1400 cm−1, which was identified as the C‐OH bending vibration. Together with the shift in peak strengths, the lack of a discernible shift in the PVDF peak location in the XRD patterns indicates that the addition of oxygen‐functionalized graphene has caused a phase transition in the PVDF in the semi‐crystal structure. Surface hydrophobicity has also been measured using contact angle measurements. The addition of oxygen‐functionalized graphene has been seen to decrease the PVDF's contact angle, resulting in the development of a hydrophilic characteristic. These PVDF‐based materials' oil/water separation capabilities have also been evaluated. PVDF composite films were not as effective as PVDF nanofiber mats with oxygen‐functionalized graphene in the studies to separate the oil/water mixtures. The permeate flux value was determined to be 240 Lm−2 h−1, and the oil/water separation efficiency of nanofibers containing 10% (m/m) PVDF534000 combined with oxygen‐functional graphene was found to be 99%.