Electrochemical water splitting is a highly effective method for carbon-free hydrogen production. While significant efforts have been made to develop efficient and cost-effective electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), the optimization of electrode surface properties has been largely overlooked. Inadequate mass diffusion, especially at high bath voltage, hampers the energy transfer efficiency of water electrolysis. To overcome these challenges, precise design of superaerophobic/superhydrophilic electrodes can effectively separate gas bubbles from the catalyst surface and enhance mass transfer, improving overpotential and Faraday efficiency. This article underscores the importance of designing electrocatalysts with well-designed surface properties to address these challenges. It also discusses characterization techniques for evaluating surface properties and provides examples of applications for superaerophobic/superhydrophilic electrodes in energy storage and conversion systems, electrochemical biosensors, and industrial processes, etc. Overall, optimizing the surface properties of electrocatalysts holds promise for enhancing the efficiency of gas-involving reactions and energy conversion systems.