Perfluorinated substances are global and ubiquitous pollutants. However, very little is known about these substances in invertebrates, and even less in terrestrial invertebrates in particular. We analysed adult male dragonflies from six sites in South Africa for perfluoroalkyl substances (PFASs), including perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluro-n-undecanoic acid (PFUnA), perfluoro-n-dodecanoic acid (PFDoA), perfluorohexanoic acid (PFHxA), and perfluorohexane sulfonic acid (PFHxS). PFOS was detected in all individuals, with less quantifiable occurrences of the other substances. The dragonflies from the three northern sites located in farming areas had significantly lower ΣPFASs concentrations than the southern sites located closer to industrial areas (median ΣPFASs of 0.32 ng/g wm (wet mass) for North, and 9.3 ng/g wm for South). All substances except PFOS occurred at similar concentrations at all six sites when quantifiable, but PFOS dominated in the Southern sites. The highest median concentration was from Bloemhof Dam (ΣPFASs = 21 ng/g wm), which is known to be polluted by PFOS. Perfluorinated substances are not known to be manufactured in South Africa, therefore the residues detected are likely to have been derived from imported products. Odonata play a significant role in freshwater ecology. Any impacts on these aquatic and aerial predators are likely to have effects on aquatic and associated ecosystems. Further studies are required over a much larger geographic region and to investigate sources.