Electron‐catalyzed reactions induced by electrochemical methods, i. e., electrocatalytic reactions, are a focus of interest in organic chemical synthesis. Since some electrolysis parameters (current, potential and coulomb amount) can be monitored and controlled and electrochemical measurement techniques are well established, we can obtain mechanistic insights into electron‐catalyzed (electrocatalytic) reactions. Using these advantages, we have investigated radical cation vinylcyclopropane rearrangements. The desired rearrangement proceeded by a catalytic coulomb amount. The synthetic outcomes and electrochemical measurements suggested that the rearrangement proceeded at the anode region via a radical cation chain mechanism. The key to the electrocatalytic rearrangement was the structure of the substrate.