A novel series of ionic liquids have been synthesized with a new methodology. The essence of this methodology is to form the cations of ionic liquids through the complexation reactions of neutral organic ligands with metal ions, followed by the subsequent metathesis reactions of the resulting salts with anion donors. We chose N-lithiotrifluoromethanesulfonimide (Li+ Tf2N-) as a candidate for anion donors because Tf2N- anions have high thermal stabilities and weakly coordinating properties, which are crucial to the generation of less viscous and more hydrophobic ionic liquids. The transition-metal ions chosen in our investigation are Ag+ and Zn2+. The uses of these ionic liquids as the new electrolytes for electrodeposition have been demonstrated. (c) 2006 The Electrochemical Society.