The first site‐selective electrochemical alkylation of tropones is realized by reacting 2‐acetoxytropones and redox‐active‐esters. The electroreductive protocol enables the preparation of a wide range (27 examples) of mono‐ and disubstituted tropones in high yields (up to 71%) and very mild conditions. Dedicated voltammetric measurements served for the identification of 2‐acetoxytropones as a class of valuable trapping agents of nucleophilic radical species and shed light on the whole mechanistic profile. Wide tolerance towards conventional functional groups (27 examples) and application to late‐stage functionalization of bioactive compounds, emphasize the synthetic impact of the present methodology