The cleanup of spilled oil from water has always been a severe and urgent issue, which attracted great attention and interest. In this study, we reported a highly efficient large-scale blow spinning technique to fabricate fibrous oil sorbents including the polystyrene (PS) fibrous sponge and polyvinylidene fluoride (PVDF)/polystyrene (PS) composite package with ultrahigh oil adsorption capacity. The wide diameter distributions and multilevel pore structure of PS fibers were obtained by controlling the precursor solution compositions used in blow spinning. The PS fibrous sponge formed by accumulating naturally exhibited an ultralow density, whose oil adsorption capacity ranged from 74 to 440 g/g for various oils and organic solvents. To enhance the mechanical strength of the PS fibrous sponge, the PVDF/PS composite package with the sandwich structure was fabricated by alternately blow spinning. The PVDF/PS composite package possessed 2.7 times the tensile strength of the PS fibrous sponge while the oil adsorption capacity had merely a slight decrease. Moreover, the fabrication strategy of blow spinning used to produce the fibrous sponge and composite package is highly efficient, cost-effective, and environment-friendly, which is suitable for large-scale industrial production of oil sorbents and oil spill cleanup in environment protection.