A major challenge for developing rechargeable Mg-ion batteries (MIB) is the lack of suitable electrolytes. We report herein dialkyl sulfones as non-Grignard and Lewis acid-free MIB electrolytes. In particular, a dipropyl sulfone (DPSO)/tetrahydrofuran (THF) (1/1, v/v) solution with MgCl₂ salt exhibits high ionic conductivity (1.1mS cm⁻¹ at 30°C), Mg cycling efficiency (> 90 %), and anodic stability (ca. 3.0 V vs Mg). As evidenced by single crystal X-ray diffraction analysis, a novel [Mg(DPSO)₆]²⁺ cation complex balanced by two [MgCl₃(THF)]⁻ anions is identified in the DPSO/THF solution. The DPSO/THF electrolyte also enables excellent cycle performance (>300cycles) of a Chevrel phase Mo₆S₈ cathode and displays a decent compatibility with an organic cathode (3,4,9,10-perylenetetracarboxylic dianhydride, PTCDA). Along with the superior electrochemical properties of the DPSO/THF electrolyte, its innate chemical stability and eco-friendly nature make it a promising MIB electrolyte.