Electrochemically active species in aluminum (Al) electrodeposition baths using AlCl3 and less volatile solvents i.e. glymes were investigated. Raman spectroscopy revealed that all the glyme baths contained AlCl4 anions and Al-Cl-glyme cations as ionic species. Room temperature conductivities were as high as the order of 10(-3) S cm(-1) for the diglyme (G2), triglyme (G3) and tetraglyme (G4) baths, whereas that for the butyl diglyme (butylG2) bath was only 10(-4) S cm(-1) due to a lower concentration of ionic species. Surprisingly, electrochemical measurements showed that, among the glyme baths, only the G2 bath enabled electrodeposition of Al. Consequently, despite the similar structures of Al-Cl-glyme complex cations, only the G2 complex cations are electrochemically active. This suggests that the desolvation of glymes from Al-Cl-glyme cations and their subsequent reduction is exceptionally easy for the G2 complexes. (C) 2016 Elsevier Ltd. All rights reserved.