Carbocations, carbon radicals, and carbanions are important reactive carbon intermediates in organic chemistry, and their interconversions can be carried out by redox processes. Although, such relationships have been well recognized, experimental work has been limited to analytical studies on highly stabilized intermediates. In this study such interconversions were examined using electrochemical reduction of "cation pools". Acyliminium cations, which were generated by low-temperature electrolysis of carbamates, were reduced electrochemically in the absence of radical acceptors. The homo coupling products formed effectively, suggesting that the one-electron reduction of the acyliminium cation produced the corresponding carbon-centered radical. Next, the electrochemical reduction of the acyliminium cations in the presence of electron-deficient olefins was examined. The cross coupling products were obtained in good-to-moderate yields. A mechanism involving radical addition to the double bond followed by the reduction of the resulting radical to the carbanion was suggested. The overall transformation serves as redox-mediated formal addition of C-H to C=C. The present strategy opens new opportunities to manipulate reactive carbon species using redox processes in organic synthesis. Copyright © 2002 American Chemical Society.