Extrafloral nectar (EFN) is a predictable and renewable resource for many ant colonies, and different ant species compete strongly to obtain and monopolize this highly nutritious food resource. Despite the importance of competition in structuring patterns of ant–plant interactions, this biological mechanism has been largely ignored in studies involving ant–plant networks. In this study we investigate the role of ant dominance hierarchy in structuring an ecological network involving ants and EFN‐bearing plants in a tropical coastal environment in Mexico. We show that within a nested ant–plant network, ant species found in the central core of highly interacting species were competitively superior, showing massive recruitment and resource domination, compared with peripheral species with fewer interactions. Moreover, we also observed that both central and peripheral ant species have the ability to quickly find the food resource. However, after 2 h of observation, central ant species are more frequently collected on the food resource when compared with peripheral species. We hypothesize that the existence of a central core of competitive ant species may indicate that most plant species found within ant–plant networks could be better protected against herbivory by these dominant ant species. In short, our results highlight the importance of competition and monopolization in the resource use by ants in the maintenance of the nested pattern in ant–plant mutualistic networks. © 2014 The Linnean Society of London, Biological Journal of the Linnean Society, 2014, 113, 405–414.