Density functional theory calculations of chemical interactions of lubricant additives sodium pyrophosphate (Na4P2O7) and orthophosphate (Na3PO4) on nascent iron Fe(110) and iron oxide Fe2O3(0001) surfaces have been carried out. Comparisons of adsorption behaviors of the two lubricant additives on different surfaces have been implemented on the basis of the thermodynamics of adsorption and electronic structure analyses. The results indicate that sodium phosphates chemically adsorb on iron and iron oxide surfaces by forming Fe–O bonds and stick on the surfaces through Fe–O–P linkages. The stronger binding of Na3PO4 than that of Na4P2O7 on both Fe(110) and Fe2O3(0001) surfaces is consistent with its better antiwear performance observed by the experiments. It is found that Fe–O bonds formed during the phosphate adsorption are stable covalent bonds that are as strong as P–O bonds of the Fe–O–P linkages. However, the binding of Fe–O–P on Fe surface is caused by a donor–acceptor mechanism; in contrast, the donation/back-donation interaction mechanism on the Fe2O3 surface. This study provides an in-depth understanding of the early stage of the tribochemical reaction between polyphosphates and metal/oxide surfaces.