Aromatic amines, crucial organic entities, exist in drugs, natural products, organic materials, and catalysts. The introduction of amines to aromatics without using metal catalysts and chemical oxidants poses a formidable challenge. Recent years have witnessed extensive developments in the oxidative aromatization of aniline. In this context, we present the electrochemical cross-dehydrogenation aromatization (ECDA) reaction involving cyclohex-2-enone and amines, culminating in the synthesis of 1,4-phenylenediamine, devoid of supplementary metal catalysts and chemical oxidants. The broad applicability of the reaction substrate is underscored, demonstrating its compatibility with select natural and pharmaceutical molecules, thus showing considerable potential for the synthesis of bioactive compounds. The mechanistic underpinnings of the reaction were probed using online electrochemical mass spectrometry.