Lubrication properties of imidazolium and phosphonium bis(oxalato)borate ionic liquids (ILs) are compared in a reciprocating sliding contact at 80 °C and 140 °C. Both the influence of the alkyl chain length and the cation architecture on friction, wear and lubricant breakdown are investigated. Imidazolium ILs showed lower friction than phosphonium ILs though only phosphonium-based ILs reduced wear. A longer alkyl chain reduced friction only in the case of the imidazolium-based ILs. Analysis of the wear scars was consistent with chemical breakdown solely of the anion. Chemical changes in the ILs after the tribotests were more pronounced for imidazolium-based ILs, and comparison of breakdown and tribofilm formation implicated catalysis by the imidazolium center, which, in turn, had a strong dependence on the surface self-assembly.