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. Here, we report a highly selective method for 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 easily reusable graphite felt electrodes, simple electrochemical device and mild conditions enables the reaction to maintain good efficiency even when scaled up to kilogram level production.