The acquisition of liquid energy sources and basic chemicals from washing water via Kolbe electrolysis is of great significance for achieving the goal of carbon-neutrality. However, the oleophilic products tend to adhere to Platinum (Pt) electrode, which results in a shortened working life of the Kolbe electrolysis. To address these issues, a novel method for endowing carbon fiber paper electrodes with underwater superoleophobic properties through simple electrodeposition is reported herein. The underwater superoleophobic electrodes improve the efficiency of the Kolbe electrolysis reaction, as oleophilic products can be easily removed from the electrode surface, thereby exposing more active reaction sites. Importantly, the underwater superoleophobic electrodes have fully demonstrated their advantages of excellent electrochemical performance, stability and durability. This work provides a novel approach for the design of high-performance electrodes in organic electro-catalysis.