AbstractThe understanding of areas for “classical” electrochemistry (including catalysis, electrolysis and sensing) and bio‐electrochemistry at the micro/nanoscale are focus on the continued performance facilitations or the exploration of new features. In the recent 20 years, a different mode for driving electrochemistry has been proposed, which is called as bipolar electrochemistry (BPE). BPE has garnered attention owing to the interesting properties: (i) its wireless nature facilitates electrochemical sensing and high throughput analysis; (ii) the gradient potential distribution on the electrodes surface is a useful tool for preparing gradient surfaces and materials. These permit BPE to be used for modification and analytical applications on a micro/nanoscale surface. This review aims to introduce the principle and classification of BPE and BPE at micro/nanoscale; sort out its applications in electrocatalysis, electrosynthesis, electrophoresis, power supply and so on; explain the confined BPE and summarize its analytical application for single entities (single cells, single particles and single molecules), and discuss finally the important direction of micro/nanoscale BPE.