We systematically investigated the electronic structure of Ru nanoparticles supported on various local structures on reduced graphene oxide (rGO) by first-principles-based calculations. We showed that Ru nanoparticles prefer to nucleate at these localized defect structures on rGO, which act as strong trapping sites for Ru nanoparticles and inhibit their aggregation. The binding of Ru nanoparticles to rGO, which is dependent on these local defect structures and correlates with the interfacial charge transfer, determines the electronic structure of the composites. Further study reveals that the performance of these composites against oxygen adsorption changes proportionally with the shift of the d-band center of the nanoparticles. The correlation between the defect structures on rGO and the reactivity of the composites suggests that controlled modification of the graphenic support by defect engineering would be an efficient way to fabricate new transition metal/rGO composites with high stability and desired reactivity. This journal is © the Partner Organisations 2014.