With unique and tunable photoluminescence (PL) properties, carbon nanodots (CNDs) as a new class of optical tags have been extensively studied. Because of their merits of controllability and sensitivity to the surface of nanomaterials, electrochemical methods have already been adopted to study the intrinsic electronic structures of CNDs. In this review, we mainly deal with the electrochemical researches of CNDs, including preparation, PL mechanism, and biosensing.