Abstract Metal alkoxides are often associated with more accessible precursors such as carboxylates, nitrates, β-diketonates in chemical routes to complex metal oxides. The molecular constitution of such solutions has been examined for systems related to ferroelectrics and based on niobium, titanium or zirconium alkoxides. A variety of oxo or non-oxo mixed-metal acetatoalkoxides have been characterized in the solid (X-ray on single crystals) as well as in solution (FT-IR, multinuclear NMR). Conversion from these molecules to the final material through hydrolysis-polycondensation has been estimated. The amorphous and crystalline powders have been characterized by thermogravimetric analysis and X-ray diffraction, respectively. Strategies for a control of the stoichiometry between the metals in the precursors are discussed. Homoleptic alkoxides Pb 6Nb 4O 4(OEt) 24 and BaTi 4(OEt) 18 were used as models for getting insight into chemical transformations.