The electrochemical codeposition of Mg-Li-Zn-Mn alloys on a molybdenum electrode in LiCl-KCl-MgCl2-ZnCl2-MnCl2 melts at 943 K (670 °C) was investigated. Preparation of the alloys by electrolysis was proven feasible in LiCl-KCl-MgCl2-ZnCl2-MnCl2 melts from cyclic voltammograms and chronopotentiometry measurements. X–ray diffraction (XRD) indicated that Mg-Li-Zn-Mn alloys with different phases were prepared via galvanostatic electrolysis. The microstructure of typical α + Mg7Zn3 phase of Mg-Li-Zn-Mn alloys was characterized by an optical microscope and scanning electronic microscopy). The analysis by energy dispersive spectrometry showed that the addition of ZnCl2 leads to the formation of intermetallic Mg7Zn3 distributed in grain boundaries, whereas Mn mainly existed on polygon particles. The results of inductively coupled plasma analysis showed that the chemical compositions of alloys were consistent with the phase structures of XRD patterns.