Noble-metal Pd and Pt catalysts with a wide range of surface wettability were fabricated through an electrochemical approach and were characterized with scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and atomic force microscopy. The importance of surface wettability of solid catalysts in multiphase reactions—especially their correlation to the nature of the studied chemical system—was investigated by reducing oxygen in an alkaline solution and oxidizing hydrogen peroxide and sodium formate in alkaline or buffered solutions at the as-prepared catalysts. These experiments illustrate that the nature of a multiphase reaction plays a critical role in determining the influence of surface wettability on the catalyst performance, providing a unique approach to decipher the reaction process. The investigation allows us to gain new insights into the electrochemical oxidation of sodium formate.