Primer pheromones play a pivotal role in the biology and social organization of insect societies. Despite their importance, they have been less studied because of the complexity of the required bioassays and, consequently, only a few of them have been chemically identified to date. The major primer pheromones are that of the queen pheromones that regulate reproductive skew and maintain colony cohesion and function. From a theoretical viewpoint, several features regarding the chemistry of queen pheromones can be predicted. They should be generally nonvolatile in order to avoid saturation of the colony space, which might otherwise hamper their perception because of sensory habituation. Accordingly, they should be actively dispersed throughout the colony by workers. The queen pheromone should also be caste-specific, qualitatively different from any worker pheromone, and preferably multicomponent, to allow unequivocal identification of the queen. The bi-potency of the female larvae in social Hymenoptera to become queen or worker necessitates strict regulation over pheromone production. Indeed, in the honeybee, the biosynthetic pathways as well as the genomic expressions are completely disparate between queens and workers. Future advances in chemical analyses, transcriptomics, proteomics, and metabolomics will enrich our understanding of the chemistry, mechanisms, and crucial role that primer pheromones play in social evolution.