The form and the interaction of species in precursor solutions for DSA-type electrocatalysts preparation have been investigated. These factors correlation with the real composition and structure of these oxide electrodes, characterized by XDA, TEM, SEM, XPS and IRS has been found. The great degree of the original metal salt hydrolysis and the formation of hydrated oxide intermediates have been revealed. Participation of hydrated oxide forms at the hydrolytic as well as the pyrolytic stage of coating formation is the general and the most typical feature that determines the composition and structure of all investigated oxide electrodes.