We provide a list for the ants collected in the leaf litter, soil and vegetation of the Parque Estadual São Camilo, an important conservation unit of Atlantic Forest in Paraná, Brazil, and one of the oldest in the state. We report 108 species, of which eight species and two genera represent new records for Southern Brazil. Seven species are reported for the first time in Paraná. Our work is the first ant list for the western limit of the state, and reveals a surprisingly high number of species considering the extension of the study area. We highlight the importance of integrating different sampling techniques to explore ant diversity, and to conduct baseline studies in protected areas to document biodiversity.