In this paper we reported for the first time the electrochemical behavior of thiolate-based solutions (RSMgCl)n-AlCl3/THF (R=4-methyl-benzene, p-isopropylbenzene, 4-methoxybenzene, n=1-2), formed from the reaction between RSMgCl and AlCl3 in THF, as electrolyte for rechargeable magnesium batteries. The solutions were characterized in term of conductivity, anodic stability, and reversibility of magnesium deposition and dissolution. Furthermore, the compatibility of the solutions with Mo6S8 cathode material was verified. Simple preparation, high cycling reversibility, moderate anodic stability, air insensitive character and the reversible electrochemical process of Mg intercalation into Mo6S8 cathode indicate the feasible application as the electrolyte for rechargeable magnesium batteries.