Numerous cancers develop years after subjects have been exposed to chemical compounds. Thus, environmental epidemiological studies need to accurately reconstruct exposures over long periods. To estimate exposure to NO2 and PM10 concentrations, we modelled ground-level air concentrations, at very fine temporal (1 h) and spatial (10 m) resolutions, over a large European metropolitan area and at subject’s address of a French national cohort, for five different years (1990, 1995, 2000, 2005 and 2010). Model performances were assessed by comparing the annual modelled concentration against monitoring station measurements. As input data, we used background concentrations from a large-scale dispersion model. The relevance of our approach was assessed by comparing results in 2010, with a modelling using monitoring values as background data. The comparison with measurement data showed good performance of the model for the majority of the period, with a performance declined in 1990. Concentrations at the subject’s residence decreased by 45% for PM10 and 38% for NO2. The proportion of subjects exposed above the WHO recommendations declined from 100% to 50% for PM10 and from 79% to 16% for NO2. The results of this study would provide a reference for future models to assess chronic exposures to PM10 and NO2 on a larger scale.