Some fire ants of the genus Solenopsis have become invasive species in the southern United States displacing native species by competition. Although the displacement pattern seems clear, the mechanisms underlying competitive advantage remain unclear. The ability of ant workers to produce relatively larger amount of alarm pheromone may correspond to relative greater fitness among sympatric fire ant species. Here we report on quantitative intra-specific (i.e. inter-caste) and inter-specific differences of alarm pheromone component, 2-ethyl-3,6-dimethylpyrazine (2E36DMP), for several fire ant species. The alarm pheromone component was extracted by soaking ants in hexane for 48 h and subsequently quantified by gas chromatography-mass spectrometry at single ion monitoring mode. Solenopsis invicta workers had more 2E36DMP than male or female alates by relative weight; individual workers, however, contained significantly less pyrazine. We thus believe that alarm pheromones may serve additional roles in alates. Workers of Solenopsis richteri, S. invicta, and hybrid (S. richteri × S. invicta) had significantly more 2E36DMP than a native fire ant species, Solenopsis geminata. The hybrid fire ant had significantly less 2E36DMP than the two parent species, S. richteri and S. invicta. It seems likely that higher alarm pheromone content may have favored invasion success of exotic fire ants over native species. We discuss the potential role of inter-specific variation in pyrazine content for the relationship between the observed shifts in the spatial distributions of the three exotic fire ant species in southern United States and the displacement of native fire ant species.