The effect of ionic liquid (IL) lubrication for aluminium/steel systems is highly dependant on the applied load and the IL structure. This study illustrates that a change in anion of an IL lubricant results in different physicochemical properties that will alter its performance at a given load. As the load is increased there is a shift in lubricant performance and mechanism of the IL. Up to a load of 30 N the lowest wear coefficient was achieved by a phosphonium diphenylphosphate IL, whilst above 30 N a phosphonium bis(trifluoromethanesulfonyl)amide IL was able to form a more tenacious tribolayer that resulted in the lowest wear.