Social insect are profoundly influenced by primer pheromones (PPhs), which are efficient means for maintaining social harmony in the colony. PPhs act by affecting the physiology of the recipients with a subsequent shift in their behavior, and many PPhs have a releaser effect (i.e., changing the probability of performing a certain behavior upon perception). In this review we try to clarify the interplay between such dual pheromonal effects. Only a few PPhs have been identified, and we provide evidence for their existence in multiple species of social Hymenoptera, which is the most extensively studied of the social insects. We focus on the regulation of reproduction, social policing, and task allocation. Considering PPhs in a broad sense, we also discuss fertility signals and the role of cuticular hydrocarbons as putative PPhs. Identification of the underlying chemistry of PPhs offers insights into insect physiology and the evolution of social behavior. PPhs of the honey bee are used to demonstrate the complexity of pheromonal communication in social insects.