To meet the challenges of global oil spills and oil-water contamination, the development of a low-cost and reusable sorbents with good hydrophobicity and oleophilic nature is crucial. In this study, functionalized carbon nanotubes (CNTs) were wrapped in polystyrene (PS) polymer (PS-CNTs) and electrospun to create an effective and rigid sorbent for oil. Covalent modification and fluorination of CNTs improved their dispersibility and interfacial interaction with the polymer, resulting in a well-aligned CNTs configuration inside the porous fiber structure. Interestingly, the oil sorption process using PS-CNTs was observed to have two phases. First, the oil swiftly entered the membrane pores formed by interconnected nanofibers due to oleophilic properties of the micro-sized void. In the second phase, the oil not only moved to nano interior spaces of the fibers by capillary forces but also adsorbed on the surface of fibers where the latter was retained due to Van der Waals force. The sorption process fits well with the intra particle diffusion model. Maximum oil sorption capacity of the PS-CNTs sorbent for sunflower oil, peanut oil, and motor oils were 116, 123, and 112 g/g, respectively, which was 65% higher than that of the PS sorbent without CNTs. Overall, a significant increase in the porosity, surface area, water contact angle, and oleophilic nature was observed for the PS-CNTs composite sorbents. Not only did the PS-CNTs sorbents exhibited a promising oil sorption capacity but also showed potential for reusability, which is an important factor to be considered in determining the overall performance of the sorbent and its environmental impacts.