A series of alloys have been electrodeposited from a melt containing ∼0.1 mol/liter Cr2+at 175°C. The alloy composition and structure were functions of the deposition potential. Depending upon the specific deposition parameters, the deposit microstructure consisted of the compound, metallic glass, and/or an fcc phase. The Cr2+ concentration was monitored by voltammetric analyses of the quasi‐reversible Cr2+/Cr3+ couple, carried out at high sweep rates due to the limited solubility of Cr3+. Specular alloys were also deposited from a room temperature melt.