Ten ionic liquids (ILs) based on glycine cations with bis(trifluoromethanesulfonyl)amide or alkylsulfate anions as novel electrolytes are prepared and evaluated. The ILs exhibit wide electrochemical windows of 5.0V and good ionic conductivity (up to 1.44mS cm −1 at 35°C). The Stokes–Einstein products of two organometallic redox couples, Fc/Fc + (ferrocene/ferrocenium) and Cc/Cc + (cobaltocene/cobaltocenium), and an organic redox couple TMPD (N,N,N′,N′-tetramethyl-para-phenylenediamine) in the ILs are determined. The solvodynamic radii of Fc, Cc, and TMPD are found to be independent of the types of ILs.