Cold rolling emulsion contains a variety of functional additives, which often exhibit complex interactions with each other. Sodium alkane sulfonate (SAS) is a common corrosion inhibitor used in cold rolling emulsions for temporary rust prevention. In this study, it was found that SAS would deteriorate the tribological properties of the emulsion. Emulsions containing SAS and different friction modifiers were prepared. Tribology tests were carried out on a four-ball friction and wear tester. White light interferometer was used to investigate the 3D morphology of the friction surface and wear volume. Microscopic morphology of friction surfaces was observed using a scanning electron microscope (SEM). The chemical activity and electrostatic potential of the molecules were calculated based on density functional theory (DFT). The adsorption energies of additives on metal surfaces were calculated via molecular dynamics (MD) simulation. The results indicate that the strong electrostatic force gives SAS an advantage in competitive adsorption with ester friction modifiers due to the positive charge on the metal surface. This results in the friction modifier not functioning properly and the tribological properties of the emulsion being significantly reduced.