Oil spills cause serious environmental pollution and serious waste of resources, hydrophobic porous absorbent has been deemed as a simple, low-cost, efficient and environment-friendly in oil-water separation. In this paper, a facile emulsion template method was developed to fabricate an interconnected porous poly(DVB-MMA) sponge. A novel co-Pickering stabilization system of Span 80 and NiFe2O4 nanoparticles was applied to fabricate ultra-concentrated internal phase W/O emulsions. After further polymerization, the resulting sponge showed excellent adsorption selectivity due to superhydrophobicity and superlipophilicity. Also, the characterization results exhibited that the composite had superior thermal stability, low density, high porosity and flexible three-dimensional porous structure. Besides, waste PS plastic was introduced to enhance the structural integrity of composite, and the addition of NiFe2O4 provided the material with magnetic operability. High oil adsorption capacity (up to 44.3-101.0 g/g), high oil retention, fast adsorption rate and superior recyclability allowed the material to be used in the fields of oil-water separation and oil pollution treatment.