1,6-Dicarbonyl compounds are versatile building blocks for the construction of pharmaceutically and biologically active heterocycles and carbocycles; yet, their efficient synthesis remains a challenge. Herein, a straightforward and efficient route for the synthesis of 1,6-diketones via electrochemical homocoupling of ketenes is disclosed. This electro-reductive approach shows a broad substrate scope without the need for metal catalysts or ligands. Moreover, the proposed mechanism was convincingly established by a series of experiments and DFT calculations.