A bipolar electrode (BPE) is an electron conductor that is embedded in the electrolyte solution without the direct connection with the external power source (driving electrode). When the sufficient voltage was provided, the two poles of BPE promote different oxidation and reduction reactions. During the past few years, BPEs with wireless feature and easy integration showed great promise in the various fields including asymmetric modification/synthesis, motion control, targets enrichment/separation, and chemical sensing/biosensing combined with the quantitative relationship between two poles of BPE. In this perspective paper, we first describe the concept and history of the BPE for analytical chemistry and then review the recent developments in the application of BPEs for sensing with ultrahigh current efficiency (η_c = i_BPE/i_channel) including the open and closed bipolar system. Finally, we offer the guide for possible challenge faced and solution in the future.