Wettability is an important property of solid surfaces, superwetting materials can be prepared by controlling the surface morphology and surface energy. In recent years, superwetting materials have been researched and used widely in the fields of self‐cleaning, anti‐fogging, microfluidics, and oil–water separation, but few studies about superwetting materials in chemical reactions have been conducted. In the multiphase reaction, the low solubility and diffusion rate of gas lead to inferior mass transfer, which restricts the reaction kinetics and reduces the reaction rate. Therefore, it may be a breakthrough to make the solid surface obtain underwater superaerophilicity. In this paper, 1H,1H,2H,2H‐perfluorooctyltriethoxysilane (POTS) with low surface energy was constructed on the palladium‐carbon nanotubes (Pd‐CNTs), as‐prepared Pd‐CNTs/POTS composite has excellent hydrophobicity and underwater superaerophilicity. When Pd‐CNTs/POTS composite was utilized in the catalytic hydrogenation, Pd‐CNTs/POTS composite shows higher catalytic activity than Pd‐CNTs; the higher catalytic performance is attributed to the underwater superaerophilicity, which enables gaseous hydrogen to rapidly accumulate on the surface of material, increasing the gas–liquid–solid reaction interface formed. The strategy looks forward to providing a new way for developing novel and efficient heterogeneous catalysts and reaction systems.