Although research on the activation of C─H bonds in alkanes has been ongoing for decades, there are still few strategies that are both highly selective and suitable for industrial production. Herein, we report a highly selective method for the chlorination of terminal C─H bonds in alkanes by combining electrochemistry and organocatalysis. The specific cavity size of organic molecular catalysts ensures high regioselectivity, while the use of inexpensive and readily reusable graphite felt electrodes, a simple electrochemical device, and mild conditions enables the reaction to maintain good efficiency even when applied to kilogram-scale production.