Lightweight alloys substitute steel in a wide range of industrial applications. It is still unclear whether the lubricant additives currently employed to reduce friction of sliding metallic parts are also efficient on non-ferrous substrates. In particular, the functionality of zinc dialkyldithiophosphates (ZDDPs) in contact with Al- and Mg-containing alloys still needs to be understood. In this work, we describe the properties of ZDDP at Al(111), Al(001), Al(331), Mg(0001) and Mg17Al12 surfaces and interfaces. Our calculations indicate that molecular fragments originated from ZDDP chemisorb more strongly on the intermetallic phase Mg17Al12 with respect to aluminum and magnesium, due to the higher surface energy of the mixed substrate. Ab initio molecular dynamics simulations show that the kinetics of the additive decomposition is significantly different on Al and the mixed phase. These results are supported by atomic force microscopy sliding tests, which revealed that the tribofilm formation is observed only on the latter substrate. This work suggests that the tribological performance of lightweight alloys can be enhanced by increasing the additive-surface chemical interactions. Display omitted •Chemistry of lightweight alloys governs the efficiency to form ZDDP-based tribofilms.•AIMD and AFM show that ZDDP cannot efficiently decompose on aluminum surfaces.•The decomposition of ZDDP on the mixed Mg17Al12 phase is instead favorable.•Affinity between S and Mg atoms drives the initial step of the tribochemical reaction