There is a constant need for discovering novel sources of compounds with antimicrobial properties, and recent studies support that symbiotic associations involving chemically mediated interactions may be a prominent source of novel compound discovery. Here I review a particularly promising natural system involving such interactions, the multipartite fungus-growing ant symbiosis. This includes a review of the ancient symbiosis involving intricate interactions between at least six symbionts, a review of the efforts that have been made in examining host-symbiont and symbiont-symbiont interactions, as well as the efforts made in identifying and characterizing chemical compounds mediating these interactions. Finally, I outline the prospects for future natural product discoveries from the system, touching on how advances in chemical analyses and whole-genome sequencing techniques will facilitate the process of natural product discovery of biomedical interest.