Traditional exposure studies that link concentrations with population data do not always take into account the temporal and spatial variations in both concentrations and population density. In this paper we present an integrated model chain for the determination of nation-wide exposure estimates that incorporates temporally and spatially resolved information about people's location and activities (obtained from an activity-based transport model) and about ambient pollutant concentrations (obtained from a dispersion model). To the best of our knowledge, it is the first time that such an integrated exercise was successfully carried out in a fully operational modus for all models under consideration. The evaluation of population level exposure in The Netherlands to NO2 at different time-periods, locations, for different subpopulations (gender, socio-economic status) and during different activities (residential, work, transport, shopping) is chosen as a case-study to point out the new features of this methodology. Results demonstrate that, by neglecting people's travel behaviour, total average exposure to NO2 will be underestimated by 4% and hourly exposure results can be underestimated by more than 30%. A more detailed exposure analysis reveals the intra-day variations in exposure estimates and the presence of large exposure differences between different activities (traffic > work > shopping > home) and between subpopulations (men > women, low socio-economic class > high socio-economic class). This kind of exposure analysis, disaggregated by activities or by subpopulations, per time of day, provides useful insight and information for scientific and policy purposes. It demonstrates that policy measures, aimed at reducing the overall (average) exposure concentration of the population may impact in a different way depending on the time of day or the subgroup considered. From a scientific point of view, this new approach can be used to reduce exposure misclassification.