Magnesium underpotential deposition on gold electrodes from magnesium nitrate –ammonium nitrate melts has been investigated. Linear sweep voltammetry and potential step were used as electrochemical techniques. Scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and X-ray diffraction (XRD) were used for characterization of obtained electrode surfaces. It was observed that reduction processes of nitrate, nitrite and traces of water (when present), in the Mg underpotential range studied, proceeded simultaneously with magnesium underpotential deposition. There was no clear evidence of Mg/Au alloy formation induced by Mg UPD from the melt made from eutectic mixture [Mg(NO3)2·6H2O + NH4NO3·XH2O]. However, EDS and XRD analysis showed magnesium present in the gold substrate and four different Mg/Au alloys being formed as a result of magnesium underpotential deposition and interdiffusion between Mg deposit and Au substrate from the melt made of a nonaqueous [Mg(NO3)2 + NH4NO3] eutectic mixture at 460 K.