Rapid industrial development has led to increased crude oil extraction and oily wastewater discharge. Achieving oil–water separation and marine oil adsorption in a cost-effective, efficient, and environmentally friendly manner remains a global challenge. In this work, natural wood was chemically treated to prepare a degradable and environmentally friendly wood sponge structure. In situ polymerization and spraying methods were used to produce an environmentally friendly oil–water separation sponge with superhydrophobic and superoleophilic properties (Fe3O4@P-P@WS). Fe3O4@P-P@WS had excellent superhydrophobicity (WCA = 154.2°) and self-cleaning properties. Additionally, Fe3O4@P-P@WS could convert solar and electrical energy into thermal energy, reaching a surface temperature of 74 °C under sunlight irradiation with an intensity of 1.0 kW m−2. When a voltage of 9 V was applied, the surface temperature reached 120.5 °C. Moreover, under the suction of a vacuum pump or the action of gravity, the continuous separation of highly fluid oil substances was achieved. The designed Fe3O4@P-P@WS offers advantages such as easily obtained raw materials, energy efficiency, simple preparation, and the ability to solve secondary pollution issues, providing a new technology for cleaning organic matter in industrial wastewater discharge and for round-the-clock cleaning of high-viscosity crude oil leaked during offshore oil exploitation.