Ant (Hymenoptera: Formicidae) assemblages were sampled with pitfall traps in three different habitats associated with a rehabilitated mine district and in undisturbed forests in Tuscany, Italy. The four habitats were (1) open fields (3–4 years old); (2) a middle-age mixed plantation (10 years); (3) an old-age mixed plantation (20 years); and (4) an oak woodland (40 years) not directly affected by mining activities. The aim of the study was to analyze ant recolonization patterns in order to provide insights on the use of Mediterranean ant fauna as indicators of restoration processes. Species richness and diversity were not significantly different among the four habitats. However, multivariate analyses showed that the assemblages in the different habitats were clearly differentiated, with similarity relationships reflecting a successional gradient among rehabilitated sites. The observed patterns of functional group changes along the gradient broadly accord with those of previous studies in other biogeographic regions. These were (1) a decrease of dominant Dolichoderinae and opportunists; (2) an increase in the proportion of cold-climate specialists; and (3) the appearance of the Cryptic species in the oldest plantations, with a maximum of abundance in the woodland. In conclusion, the results of our study supported the use of Mediterranean ants as a suitable tool for biomonitoring of restoration processes, and in particular, the functional group approach proved a valuable framework to better interpret local trends in terms of global ecological patterns. Further research is, however, needed in order to obtain a reliable classification of Mediterranean ant functional groups.