Superhydrophilic and underwater superoleophobic materials have demonstrated good application prospects in the oil/water separation. However, their fabrication process may be inefficient and high energy consumption. For this reason, this paper proposes a method for simultaneously deposited hierarchical structures with superhydrophilic and underwater superoleophobic properties on the anode and cathode via one-step electrodeposition. The materials fabricated on both anode and cathode exhibit superior antifouling performance and excellent oil/water separation efficiency (above 96.2% for all five experimental oils) with a considerable permeation flux (4125 ± 67 L m−2 h−1). Moreover, the as-prepared materials maintain excellent oil/water separation efficiency after 20 separation cycles, which are higher than 98.1% and 98.8%, respectively. Besides, the materials can be stored in different concentrations of salt water for 50 days, demonstrating their outstanding corrosion resistance. Our study provides a strategy for the fabrication of superwetting materials, which is expected to promote the development of oil/water separation technology.