Mutualistic networks involving plants and their pollinators or frugivores have been shown recently to exhibit a particular asymmetrical organization of interactions among species called nestedness: a core of reciprocal generalists accompanied by specialist species that interact almost exclusively with generalists. This structure contrasts with compartmentalized assemblage structures that have been verified in antagonistic food webs. Here we evaluated whether nestedness is a property of another type of mutualism—the interactions between ants and extrafloral nectary-bearing plants—and whether species richness may lead to differences in degree of nestedness among biological communities. We investigated network structure in four communities in Mexico. Nested patterns in ant–plant networks were very similar to those previously reported for pollination and frugivore systems, indicating that this form of asymmetry in specialization is a common feature of mutualisms between free-living species, but not always present in species-poor systems. Other ecological factors also appeared to contribute to the nested asymmetry in specialization, because some assemblages showed more extreme asymmetry than others even when species richness was held constant. Our results support a promising approach for the development of multispecies coevolutionary theory, leading to the idea that specialization may coevolve in different but simple ways in antagonistic and mutualistic assemblages.