In the tropics, several ant species are obligate inhabitants of leaf pouches and other specialized structures in plants known as myrmecophytes. However, the cues used by ant queens to locate suitable host-plants following dispersal remain poorly understood. Here we tested the hypothesis that Pheidole minutula queens use volatiles to distinguish their host Maieta guianensis (Melastomataceae) from other sympatric myrmecophytes. To do so, we used a Y-tube olfactometer to quantify the preference for volatiles of different plant species. Our results indicate that P. minutula queens discriminate the chemical volatiles produced by its host-plant from those of other sympatric ant-plant species. However, queens failed to distinguish the volatiles of Maieta from those of the ant-plant Tococa bullifera (Melastomataceae), with which P. minutula is not mutualistically associated. Nevertheless, a strong preference for Maieta over Tococa was observed during a subsequent bioassay, where the ants had physical contact with a domatium of each plant species. These results suggest that additional, short distance mechanisms are also necessary for host discrimination. Overall, our findings suggest that the high degree of compartmentalization observed in symbiotic ant-plant relationships is achieved, at least in part, by the relatively high degree of specificity in host selection displayed by foundress queens.