Semiochemicals play a vital role within and among colony interactions, and they also mediate interactions between honey bees and their parasites and predators. In this section, we describe methods used to collect and analyse volatiles from honey bees in their native environments. The discussion focuses on in situ collection of volatiles because natural emission rates are the most biologically relevant metric of volatile characterization. While volatile collection and analysis techniques are described broadly, these methods are specifically discussed in the context of working with a hive and its inhabitants. Given the complexity of honey bee chemical interactions, the authors strongly emphasize that detection of a compound in the gaseous phase does not confirm activity of the compound in that phase (see Keeling et al., 2003, on contact activity of volatile queen retinue pheromone components). Researchers use bioassays to determine the mode of biological activity for volatiles collected from honey bees (Torto et al., 2007b). In situ analytical methods are most informative when used in tandem with other methods to characterize volatiles. In particular, ex situ volatile collection (see section 3 of this paper) and chemical analysis of tissue extracts (see sections 4 and 6) can be used to specifically identify the odour source in the colony and within the bee itself.