By y-irradiation a t 77" K of the Cul'-containing organic crystals, Cu(CH,CN),C10,, Cu(HOOCCH,CH,CN),C10,, and Cu(CH,CN),BF,, Cu2' centres in near-tetrahedral field were produced. These Cu2+ centres approximated the electron spin resonance characteristics ( IAl; 1 . = 0.008 cm-l) and light absorption of Cu2+ in Cu-containing oxidoreductases. No exact correlation was found between the g-values of the model system and the Cu-oxidases. It is suggested that the Cu site in these enzymes is intermediate between the square planar (normal for Cu2+) and the tetrahedral (normal for Cul+) configuration, which makes it suited for rapid electron transport.