We have investigated, using density functional simulations, the energetics and the electronic properties of oxides of selected transition metals, TMs, adsorbed onto a dia-mond (001) surface. We find that stoichiometric oxides of TMs, particularly Ti and Zn,influence the electron affinity of diamond strongly. The electron affinities of stoichiomet-ric oxides of Ti and Zn are calculated to be around −3 eV, significantly higher than 1.9 eV of commonly used H–termination. The reactions of TMs with an oxygenated diamond are found to be highly exothermic. Based upon the energetics and the electronic properties, we propose that in the regime of ultra thin films, oxides of TMs are promising options for surface coating of diamond–based electron emitters, as these coatings are compatible with semiconductor device fabrication processes, while having the benefit of inducing a large negative electron affinity.