Through simple thermodynamic considerations, the metal oxides reduction reaction in polyol medium (ethylene glycol) has been addressed with the assumptions that the reaction takes place at the boiling point of the alcohol, and that the polyol is totally oxidized with formation of CO 2 and H 2 O. By considering the initial (MO x ؉ethylene glycol) and 5nal (M؉CO 2 ؉H 2 O) states, we estimated the Gibbs free energies ( G red ) for the reduction of numerous oxides, and found a good correlation with the experimental results. Without any exception, oxides leading to metallic powder when reacted in boiling polyol medium have a negative calculated G red . However, a few oxides with negative calculated G red could not be reduced to metal, likely for kinetics limitations and/or solubility issues. This strategy has been extended with similar success to both hydroxide precursors and other alcohols having longer backbones (e.g., glycerol). Finally, we show that this basic thermodynamic approach opens new insights for the synthesis of alloys, obviously represents a useful prediction tool for the preparation of metals, and could be easily extended to the preparation of oxides.