Femtosecond laser microfabrication has been recently utilized in interface science to modify the liquid wettability of solid surfaces. In this paper, a silicon surface with hierarchical micro/nanostructure is fabricated by a femtosecond laser. Similar to fish scales, the laser-induced surface shows superhydrophilicity in air and superoleophobicity underwater. The oil contact angles can reach up to 159.4 ± 1° and 150.3 ± 2°, respectively, for 1,2-dichloroethane and chloroform droplets in water. In addition, the surface exhibits ultralow oil-adhesion. In the oil–water–solid three-phase system, water can be trapped in the hierarchical rough structure and form a repulsive oil layer according to the extended Cassie's theory. The contact area between the as-prepared surface and oil droplets is significantly reduced, resulting in superoleophobicity and ultralow oil-adhesion in water. In addition, as a potential application, the working principle diagram of preventing blockage ability of underwater superoleophobic pipes is propounded.