Social insects demonstrate remarkable behavioral flexibility in response to complex external and social environments. One of the most striking examples of this adaptability is the context-dependent division of labor among workers of bees and ants. Neuropeptides, the brain's most diverse group of messenger molecules, play an essential role in modulating this phenotypic plasticity related to labor division in social insects. Integrated omics research and mass spectrometry imaging technology have greatly accelerated the identification and spatiotemporal analysis of neuropeptides. Moreover, key roles of several neuropeptides in age- and caste-dependent behavioral plasticity have been uncovered. This review summarizes recent advances in the characterization, expression, distribution, and functions of neuropeptides in controlling behavioral plasticity in social insects, particularly bees and ants. The article concludes with a discussion of future directions and challenges in understanding the regulation of social behavior by neuropeptides.