The utilization of tetraethylammonium perfluorobutane sulfonate as a promising alternative salt for electrolyte solutions in electrochemical double layer capacitors is introduced in this study. A thorough analysis of the physical and electrochemical characteristics of tetraethylammonium perfluorobutane sulfonate was conducted, including the assessment of its ionic conductivity, viscosity, and thermal behavior, using a 1 M solution in acetonitrile. Comparative assessments were made between the performance of this novel electrolyte and two well‐studied electrolytes: 1 m tetraethylammonium tetrafluoroborate and 1 m tetraethylammonium bis(trifluoromethanesulfonyl)imide in acetonitrile, focusing on electrochemical performance and long‐term stability. Furthermore, an investigation into the impact of tetraethylammonium perfluorobutane sulfonate on the anodic dissolution of aluminum current collectors was conducted. The results highlight the potential of tetraethylammonium perfluorobutane sulfonate as an effective replacement for bis(trifluoromethanesulfonyl)imide‐based electrolytes.