We report the first synthesis of aluminum hexafluorophosphate (Al(PF6)3) and its electrochemical properties in dimethyl sulfoxide (DMSO). The single crystal structure of the synthesized Al(PF6)3 is revealed as [Al(DMSO)6](PF6)3, and 0.25 M Al(PF6)3 in DMSO with high ionic conductivity is obtained. The purity of this electrolyte was further confirmed with nuclear magnetic resonance spectroscopy and electrospray ionization mass spectrometry. We then demonstrated the reversibility of Al deposition-stripping in this electrolyte using scanning electron microscopy and an X-ray photoelectron spectroscopy depth profiling study. The parasitic reaction involving DMSO decomposition during Al deposition is also identified via gas chromatography/electron ionization mass spectrometry.