Electrochemical reduction of phthalazines and 1,2,5-thiadiazoles containing nucleofugaceous groups at the carbon α-atoms are studied in aprotic and proton-donating media. Heteroatoms, substituents, and media are found to affect potentials and reaction path for the electroreduction. The factors determining the reductive opening of heterocycles are revealed. In diazines the heterocycle opening in annelated systems is induced by the electron transfer, provided there exist (a) a heteroatom–heteroatom bond and (b) an easily splitting-off group at the carbon α-atom, whose nucleofugacity is comparable with or exceeds that of the chloride ion. Stability of the 1,2,5-thiadiazole cycle toward its reduction is determined by the substituent and the medium nature. On adding a nucleofugaceous group to the molecule, the transfer of two electrons in an aprotic medium results in the heterocycle opening with the formation of iminonitrile; when two easily splitting-off groups are present, the electron transfer makes the cycle decompose into inorganic anions.