AbstractESR spectra of the radical anions obtained from 1,4,5,8‐tetraazanaphthalene by electrolytic and chemical reduction have been recorded. The hyperfine structure of the electrolytically generated anion (solvent: N,N‐dimethylformamide; counter‐ion: tetraethylammonium) is that of an unassociated species, whereas evidence of strong ion‐pairing can be derived from the spectra of the chemically prepared anions (solvent: 1,2‐dimethoxyethane; counter‐ion