The solid-liquid phase diagram of the (1-ethyl-3-methylimidazolium bis{(trifluoromethyl) sulfonyl} amide + benzene) system was determined and allowed us to identify and characterize an equimolar inclusion compound, [emim][NTf2].C6H6, with a congruent melting temperature: this type of behaviour, reported here for the first time, together with the X-ray structure of the inclusion compound lays emphasis upon the interactions that are responsible for the existence of liquid clathrates at higher benzene concentrations.