The use of electric current in synthetic organic chemistry offers a sustainable tool for the selective reductive synthesis of quinoline N‐oxides starting from easily accessible nitro compounds. The reported method employs mild and reagent‐free conditions, a simple undivided cell, and constant current electrolysis set‐up which provides conversion with a high atom economy. The synthesis of 30 differently substituted quinoline N‐oxides was successfully performed in up to 90 % yield. Using CV studies, the mechanism of the selective formation of the quinoline N‐oxides was elucidated. The technical relevance of the described reaction could be shown in a 50‐fold scale‐up reaction. [ABSTRACT FROM AUTHOR]