Alkylation of heteroarenes by using aldehydes is a direct approach to increase molecular complexity, which however often involves the use of stochiometric oxidant, strong acid, and high temperature. This study concerns an energy-efficient electrochemical alkylation of heteroarenes by using aldehydes undermildconditions without mediators. Interestingly, the graphite anode can trigger aldehyde cationic
bis(5‐methyl‐2‐furyl)methanes has been achieved via the reaction of 2‐methylfuran with a series of aliphatic and aromatic aldehydes and aliphatic ketones in presence of copper(II) triflate undersolventfreeconditions. The bis(5‐methyl‐2‐furyl)methanes were obtained in 34% –72% yields and the catalyst was recycled up to four successive cycles without much loss in catalytic activity.