Odours can have a significant influence on the outcome of social interactions. However, we have yet to characterize the chemical signature of any specific social cue in human body odour, and we know little about how changes in social context influence odour chemistry. Here, we argue that adoption of emerging analytical techniques from other disciplines, such as atmospheric chemistry, might become game-changing tools in this endeavour. First, we describe the use of online chemical ionization time-of-flight mass spectrometry to sensitively measure many hundreds of gas-phase volatile organic compounds in real time. By analysing ambient air emanating from undisturbed individuals or groups, the technique enables a continuous recording of an instantaneous odour change in response to external stimuli and changing social context. This has considerable advantages over the traditional approach of periodic sampling for analysis by gas chromatography. We also discuss multivariate statistical approaches, such as positive matrix factorization, that can effectively sift through this complex datastream to identify linked groups of compounds that probably underpin functional chemosignals. In combination, these innovations offer new avenues for addressing outstanding questions concerning olfactory communication in humans and other species, as well as in related fields using odour, such as biometrics and disease diagnostics.This article is part of the Theo Murphy meeting issue ‘Olfactory communication in humans’.