Electrochemical intercalation studies are used to characterize a series of ionic liquids composed of a variety of cationic and anionic species. Electrochemically, the ionic liquids are characterized by cyclic voltammograms and charge–discharge experiments for the intercalation and de-intercalation of the various cationic and anionic species into graphite. X-ray structure analysis is also performed to determine the relationship between the electrochemical behaviour of the ionic liquids, and the formation of intercalated graphitic compounds. Two different types of imidazolium cations are studied, specifically the di- and trisubstituted imidazolium. These cations are paired with the following anions: tetrafluoroborate, hexafluorophosphate, bis(trifluoromethanesulfonyl)imide, bis(perfluoroethanesulfonyl)imide, nitrate and hydrogen sulfate. Results indicate stronger intercalation chemistry for the trisubstituted imidazoliums, correlating with the greater charge–discharge efficiencies found for these types of ionic liquids. Many of the anions exhibit very poor charge–discharge efficiencies, correlating to very poorly formed graphite intercalates. The exception to this is the hydrogen sulfate intercalate, which had low charge–discharge efficiencies but formed a well defined graphite intercalate. Only the imide based anions exhibited both high charge–discharge efficiencies and the formation of a clearly defined graphite intercalate.