Tungstate-functionalized room-temperature ionic liquids (ILs), 1-alkyl-3-methylimidazolium tungstates [RMIm](2)[WO4] (R = C6H13 or C12H25), were synthesized and the IL's structure has been proved by NMR, Fourier transform IR, and elemental analysis. The physicochemical characteristics of the tungstate-based ILs have been determined by using methods of conductivity, viscosity, and cyclic voltammetry measurements, in comparison with those of the conventional ILs such as 1-hexyl-3-methylimidazolium methanesulfonate and 1-hexyl-3-methylimidazolium hexafluorophosphate. The influences of anions and the length of alkyl chain linked to the imidazolium ring on physicochemical properties of the ILs were examined in detail. All ILs owned higher conductivities and lower viscosities at higher temperatures. The strong intramolecular hydrogen bonds were found in the tungstate-based ILs. Cyclic voltammograms of the functionalized ILs illustrated that they were quite electrochemically stable. In general, the understanding of electrochemical properties of imidazolium ILs can facilitate their possible applications in electrochemistry. (C) 2010 The Electrochemical Society. [DOI:10.1149/1.3462993] All rights reserved.