The aim of present study was to determine the role of secondary, serpentine forests in Poland in the protection of rare vascular plant species. On the basis of 95 phytosociological relevés collected between 2009 and 2020, we identified the main types of serpentine forest communities and assessed their diversity indices. Ordination methods were used to determine the relationship between the degree of transformation of forest communities (reflected by the occurrence of alien and nitrophilic species) and the presence of endangered species in their undergrowth including the environmental background. We distinguished four types of communities: thermophilic and mesophilic pine plantations (both secondary in origin) as well as thermophilous oak forest and acidophilous oak–hornbeam forest (semi-natural and close to natural in character, respectively). Rare and endangered species were unevenly distributed and concentrated in oak forest (16 species) and thermophilic pine plantation (nine species). The endangered species mainly preferred sites at higher altitudes and with higher slope inclination, light availability, and soil reaction. We did not confirm that the presence of alien or nitrophilic species negatively influenced the ability of studied forests to preserve rare plants. As secondary forests can still harbor endangered species, they should fulfil complementary functions in the nature protection system.