HypothesisIonic liquids (ILs), as lubricant additives, can greatly improve the lubricating behavior of the frictional interfaces. However, it is urgent to explore ILs with good oil solubility in nonpolar oils, and it is necessary to further study and verify the lubrication mechanism of ILs from the perspective of alkyl chain length.ExperimentsFive protic ILs (PILs) with varying alkyl chain lengths were synthesized by proton transfer method. As additives in PAO oil, their tribological properties were investigated on SRV-V tester. Through molecular dynamics simulation, the adsorption behavior of PILs at the frictional interface was illustrated.FindingsThe tribological properties of base oil could be significantly improved by adding PIL additives, but interestingly, PILs with short-chain anions showed better lubricating performance, which contradicted most of the early findings. Further analyses revealed that PILs achieved effective lubrication by the tribochemical interaction between anions and frictional interface, and the formation of cationic protective layer. However, PILs with shorter-chain anions form a denser protective layer that can better support the interfacial anions to participate in tribochemical reactions and thus abnormally exhibit superior lubricating performance than those with longer-chain anions.