A small number of Eoarchean zircon grains with ages reaching 3970 Ma (2 grains, SIMS) were recently discovered in the Mesoarchean (ca. 2.9 Ga) granites and meta-andesites in the West Azov Domain of the Ukrainian Shield. In total, 17 SIMS and LA-ICP-MS analyses yielded ages over 3700 Ma, and 9 were older than 3900 Ma. All but one of these zircon grains have negative εHf values, ranging from -1 to -11, and show a tendency towards more negative values in the younger grains. The average minimum MORB-DM model Hf age assuming Lu/Hf = 0 (i.e. Pb-loss in the zircon) is 4.2 Ga. “Felsic crust” and “mafic crust” models with Lu/Hf > 0 would result in even older model ages. Grains with the lowest εHf values have older minimum model Hf ages exceeding 4.35 Ga. Therefore, the Hf isotope characteristics of the studied zircon grains are indicative of the presence of Hadean material in the West Azov Domain of the Ukrainian Shield. On the age vs. εHf diagram, zircon from the West Azov Domain plot within the field defined by the Eoarchean to Hadean detrital zircons from Jack Hills in Western Australia, similar to zircon occasionally found in many other localities worldwide. Ukrainian zircon thus confirms the well-known phenomenon of the “evolved” Hf isotope composition of the oldest terrestrial (and lunar) zircons, which might reflect very early development of a thick, long-lived proto crust with a distinct Hf isotope signature. Nearly complete destruction of this early crust in the Eoarchean gave way to the appearance of zircon with juvenile Hf isotope compositions.