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Tribotronics represents the modulation of friction via an external electric potential, a field with promising ramifications for intelligent devices, precision manufacturing, and biomedical applications. A profound elucidation of mechanisms that allow for potential-controlled friction is foundational to further research in this tribotronic domain. This article provides a comprehensive review of the research progress in electro-controlled friction over the past few decades, approached from the perspective of the boundary lubrication film at the friction interface, a direct influencer of electro-controlled friction performance. The mechanisms of potential-controlled friction are categorized into three distinct classifications, contingent on the formation mode of the boundary lubrication film: potential-induced interfacial redox reactions, interfacial physical adsorption, and interfacial phase structure transformations. Furthermore, an outlook on the application prospects of electro-controlled friction is provided. Finally, several research directions worth exploring in the field of electro-controlled friction are proposed. The authors hope that this article will further promote the application of electro-controlled friction technology in engineering and provide intellectual inspiration for related researchers.