The chemical signature of social insects is very important for communication, and specific signs of each colony and its individuals are acquired throughout their development. This chemical signature can also be related to the composition of the materials employed during nest construction. Furthermore, the venom also contains important chemicals required for the maintenance of wasp colonies. Therefore, the objective of this study was to evaluate the chemical composition of the wasp Protopolybia exigua along its different development stages, including the nest substrate and the venom of adult worker at different ages. To achieve this, gas chromatography coupled to mass spectrometry was used. The results show that the chemical cuticular compounds present in different stages of development, and in the nest of P. exigua, are qualitatively similar, but quantitatively different, demonstrating that these compounds can be used as signals for the identification of co-specific individuals within the colonies. However, there was no significant variation in these compounds between different colonies, which may be related to the parental level between the colonies and due to them sharing the same resources. The non-polar compounds of the venom vary significantly according to the age of the workers, probably due to their different roles within the colony, and there was a clear increase in the complexity of the compounds as the wasps aged. Older wasps perform higher-risk activities, such as foraging, and therefore need to make more use of venom.