Our calculations predict that Ge alloying induces both ligand and bifunctional effects. Charge transfer phenomena and orbital hybridization between Pt and Ge alters the adsorption properties of the catalyst (structure-activity relationship) in a composition dependent fashion. Further, Pt-Ge shows a dual adsorption behavior where CO always binds to Pt sites, while oxygen shows a clear preference towards Ge due to its greater oxophilicity. Precisely, this oxophilicity of Ge makes part of it oxidize to GeO x , and consequently, a new oxygen source is developed resistant to CO poisoning. The provided results require a more thorough analysis to correctly sample the boundary between the CO poisoning and CO poisoning-free regimes as a function of pressures and temperature. As for now, this remains yet a topic of future study.