© The Royal Society of Chemistry 2014. A report is presented on the use of cyclic voltammetry using silver as a working electrode in imidazolium ionic liquids. The electrocatalytic properties of silver allow cyclic voltammetry to be turned into an ideal tool to have a simple and accurate access to diffusion coefficient values and solubility values of carbon dioxide in ionic liquids under standard conditions. Besides, the determination of the reduction peak potential values of carbon dioxide in ionic liquids also makes it possible to "energetically" quantify the benefits of using silver electrodes and imidazolium ionic liquids. The combined use of silver, as electrocatalytic material, and imidazolium ionic liquids, as a co-catalyst, enables the electrochemical reduction of CO2 to be decreased by up to 0.8 V!