The pollution arising from oil spills is a matter of great concern due to its damaging impacts on the ecological environment, which has created a tremendous need to find more efficient materials for oil spill cleanup. In this work, we reported a sorbent for oil soak-up from a water surface with a high sorption capacity, good selectivity, and excellent reusability based on the hydrophobic-oleophilic fibrous mats that were fabricated via co-axial electrospinning polystyrene (PS) solution as the shell solution and polyurethane (PU) solution as the core solution. The fine structures of as-prepared fibers were regulated by manipulating the spinning voltages, core solution concentrations, and solvent compositions in shell solutions, which were also characterized by field emission scanning electron microscopy, transmission electron microscopy, nitrogen adsorption method, and synchrotron radiation small-angle X-ray scattering. The effects of inter-fiber voids and intra-fiber porosity on oil sorption capacities were well studied. A comparison of oil sorption capacity for the single fiber with different porous structures was also investigated with the help of scanning transmission X-ray microscopy. The results showed that the sorption capacities of the as-prepared sorbent with regards to motor oil and sunflower seed oil can be 64.40 and 47.48 g g(-1), respectively, approximately 2-3 times that of conventional polypropylene (PP) fibers for these two same oils. Even after five sorption cycles, a comparable oil sorption capacity with PP fibers was still maintained, exhibiting an excellent reusability. We believe that the composite PS-PU fibrous mats have a great potential application in wastewater treatment, oil accident remediation and environmental protection.