Electrocatalysis can synthesize valuable chemicals and plays a vital role in developing clean and renewable energy storage and conversion devices. In traditional electrocatalytic systems, researchers have attempted to independently synthesize one type of valuable chemical at the cathode or anode. Recently, the electrocatalytic bipolar synthesis of valuable chemicals at both the cathode and anode has become popular and has attracted much attention. In this minireview, we summarize the latest processes on innovative strategies for the electrocatalytic bipolar synthesis of various chemicals. We will discuss the findings according to the categories of the products, including bipolar hydrogen production, bipolar formate production and bipolar hydrogenation. The associated catalyst optimization, reaction mechanism, and design principles are well described. Moreover, the challenges and prospects for future developments are highlighted. This review is timely and will guide others to pay more attention to these novel electrocatalytic bipolar synthesis systems.