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A bipolar electrode (BPE) is an electronic conductor that can promote asymmetrical reactions at two poles (one for oxidation and one for reduction) under a sufficient power supply without direct ohmic connection. Bipolar electrochemistry as a versatile approach simplifies some complicated processes, such as the easy synthesis of Janus particles, high-throughput screening/sensing and micro-swimmers. Meanwhile, the wireless feature of bipolar electrochemistry makes monitoring the Faradaic current difficult. Fortunately, electrochemiluminescence (ECL), the light emission initiated by an electrochemical reaction, as a powerful analytical tool, matches the features of bipolar electrochemistry well and can achieve the transduction of the Faradaic current flowing through the BPE easily. The chapter focuses on the fundamentals of bipolar electrochemistry, the classification of bipolar electrochemistry developed in recent years and the BPE–ECL application in sensing including DNA, RNA, peptide, biomarkers and small molecules with different detection modes. Finally, future possible opportunities will be discussed.

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