As tawny crazy ants (Nylanderia fulva) invade the southern USA, they often displace imported fire ants (Solenopsis invicta). Following exposure to S. invicta venom, N. fulva applies abdominal exocrine gland secretions to its cuticle. Bioassays reveal that these secretions detoxify S. invicta venom. Further, formic acid, from N. fulva venom, is the detoxifying agent. N. fulva exhibits this detoxification behavior after conflict with a variety of ant species; however, it expresses it most intensely after interactions with S. invicta. This behavior may have evolved in their shared South American native range. The unique capacity to detoxify a major competitor’s venom likely contributes substantially to its ability to displace S. invicta populations, making this behavior a causative agent in the ecological transformation of regional arthropod assemblages.