The formation of a built-in electric field (BIEF) can induce electron-rich and electron-poor counterparts to synergistically modify electronic configurations and optimize the binding strengths with intermediates, thereby leading to outstanding electrocatalytic performance. Herein, a critical review regarding the concept, modulation strategies, and applications of BIEFs is comprehensively summarized, which begins with the fundamental concepts, together with the advantages of BIEF for boosting electrocatalytic reactions. Then, a systematic summary of the advanced strategies for the modulation of BIEF along with the in-detail mechanisms in its formation are also added. Finally, the applications of BIEF in driving electrocatalytic reactions and some cascade systems for illustrating the conclusive role from the induced BIEF are also systematically discussed, followed by perspectives on the future deployment and opportunity of the BIEF design.