In this work, polyvinyl chloride (PVC)/clay nanofiber composites with various contents were fabricated by the electrospinning process. The morphology, porosity, density, and mechanical properties of the nanofiber mats were investigated. In addition, PVC/clay nanofiber mats were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Moreover, the influence of the clay content in the nanofiber mats and its effect on oil sorption capacity were also evaluated. The results show that the clay particle diameter affects the fabrication, morphology, porosity, density, mechanical properties, and sorption capacity of the nanofiber mats. Adding clay in nanofiber composite materials leads to higher porosity and a higher oil sorption capacity. PVC/clay nanofiber mats have a high oil sorption capacity at low temperatures. They exhibit a high potential to be used as materials to eliminate oil spills under arctic conditions.