In this account, several unique effects induced by rapid alternating polarity were discussed. First, rAP could simplify complex redox reactions by suppressing slow redox processes that could otherwise take place under conventional DC electrolysis. Second, rAP could outcompete proton reduction to enable Birch-type (hetero)arene reduction even when reduction potential of a (hetero)arene is outside the electrochemical window of the solvents. Finally, rAP could alter local pH environment around electrodes to facilitate decarboxylation of carboxylic acids. These unique effects are the foundation for the most striking feature of rAP -it dramatically alters reaction outcome simply by virtue of its differing waveform, a phenomenon that has yet to be appreciated in synthetic organic electrochemistry. As the area of waveform-controlled electrosynthesis is still in its infancy, what is described here is likely just the tip of the iceberg, and further studies are underway to uncover more unique reactions that can simplify the practice of organic synthesis.