Hafnium(IV) oxide thin films were synthesized by atomic layer deposition (ALD) on Si(100) substrates, using an innovative guanidinate-stabilized hafnium amide precursor, [Hf(NEtMe)₂(EtMeNC(NⁱPr)₂)₂]. In the present work, our attention is focused on a detailed XPS characterization of a representative HfO₂ coating grown at 350 °C. Beside the wide scan spectrum, detailed spectra for the O 1s, Hf 4f, Hf 4d and C 1s regions and related data are presented and discussed. The obtained results point out to the formation of HfO₂ coatings characterized by the presence of -OH groups, whose main origin is attributed to the use of water as oxidizing agent during the preparation process.