In order to cope with the increasing oil spill accidents and the intentional discharge of oily wastewater, a new oil-adsorbing material with superhydrophobicity and reusability is needed. In this paper, waste plastic was used to fabricate an alveolate polystyrene (PS) foam to reduce secondary pollution. The PS foam was synthesized from a high internal phase Pickering emulsion (HIPPE) technique in a one-step process. The emulsion was stabilized by a co-Pickering system of Span 80 surfactant and SiO₂ particles. To explain the super stability of the HIPPE, a novel model of the water-in-oil droplet was promoted. The obtained SiO₂@PS foam exhibited a multi-order-porous structure, and displayed superhydrophobicity and superoleophilicity. It can selectively remove various oily contaminants from water with a high adsorption capacity of 20.4–58.1 g g⁻¹ at a fast rate. The oil-adsorbed material can be reused by simple centrifugation, and no more than a 1% decline was obtained in the oil adsorption after 10 cycles. Therefore, the SiO₂@PS foam has a great potential application in oily water treatment.