AbstractThe electrochemical reduction process of fluoro‐substituted aza‐aromatics can well be described by the pattern which is normally postulated for aryl halogenides,i.e.fission of the carbon‐halogen bond. However, the stability of the intermediate mono‐negative ions is generally higher than for the comparable fluoro‐substituted arenes. As an example of this stability, the ESR spectrum of tetrafluoroquinoxaline is given. The half‐wave reduction potentials of the first reduction wave can be related to the electron affinities of the molecules. These electron affinities have been correlated with those obtained by semi‐empirical quantum‐chemic