Dynamic tribochemical processes for dicationic ionic liquid containing a germinal imidazolium cation head groups bridged by a poly(ethylene glycol) and bis(trifluoromethylsulfonyl)imide anion were studied using time-resolved Mechanically Stimulated Gas Emission Mass-Spectrometry (MSGE-MS). In comparison with similar monocationic imidazolium ionic liquids with short alkylic or long polyether side chains the dicationic ionic liquid had lower coefficient of friction on Ti6Al4V alloy and smoother behaviour. The analysis of volatile decomposition products suggested multiple tribochemical reactions in which both anionic and cationic moieties are involved. Tribochemical degradation of cations was mainly through detachment of the side and bridging chains from the imidazolium head groups. Absence of volatile products containing nitrogen implies that imidazole group remained unchanged. Hydrogen and water desorption were attributed to the reactions of hydrogen fluoride being a product of anion degradation with titanium and titanium oxide.