Over the last 2 decades, the importance of emissions source types of atmospheric pollutants in urban areas has undergone significant change. In particular, there has been a considerable reduction in emissions associated with road vehicles. Understanding the role played by different source sectors is important if effective air pollution control is to be achieved. Current atmospheric measurements are made at fixed monitoring sites, most of which do not include the measurement of volatile organic compounds (VOCs), so our understanding of the temporal and spatial variation of pollutants is limited. Here we describe the application of a mobile laboratory using a selected-ion flow-tube mass spectrometer (SIFT-MS) and other trace gas instrumentation to provide on-road, high-spatial- and temporal-resolution measurements of CO2, CH4, VOCs and other trace gases. We then illustrate the potential of this platform for developing source characterisation methods that account for the similarity in correlation between species. Finally, we consider the benefits of high-spatial- and temporal-resolution measurements in characterising different types of sources, which would be difficult or impossible for single-species studies.