Fire ants are aggressive Neotropical ants that are extensively similar in general biology and morphology, making species identification difficult. Some fire ant species are top-rated pests spreading throughout the world by trade vessels. Many researchers attempted to sort between invasive and native species by using chemical characters, including patterns of venom alkaloids. The present study is the first to report intraspecific variation in some chemical characters, namely, cuticular hydrocarbons and venom alkaloids, within the Brazilian fire ant speciesSolenopsis saevissimaand also reports on within-nest variations among members of different castes. Two different haplotypes (cryptic species) ofS. saevissimawere clearly identified, one presenting a predominant combination of the venom alkaloidscis- andtrans-2-methyl-6-undecylpiperidine with the cuticular hydrocarbons C23, 3-Me-C23, 10-C25 : 1, C25, and 3-Me-C25, and the other a predominant combination ofcis- andtrans-2-methyl-6-tridecenylpiperidine with predominance of 12-C25 : 1, C25, 11-Me-C25, 3-Me-C25, 13-C27 : 1, C27, and 13-Me-C27. Intranest variations revealed that the proportions among these compounds varied sensibly among workers of different sizes, gynes, and males (no alkaloids were detected in the latter). Larva contained vestiges of the same compounds. The recorded chemical profiles are quite different from previous reports withS. saevissimasamples from São Paulo. The finds thus support other recent claims thatS. saevissimaincludes cryptic species; the study, moreover, adds the find that they can occur in the same geographical location.