UNLABELLED: A number of studies have estimated population exposure to PM2.5 by examining modeled or measured outdoor PM2.5 levels. However, few have taken into account the mediating effects of building characteristics on the ingress of PM2.5 from outdoor sources and its impact on population exposure in the indoor domestic environment. This study describes how building simulation can be used to determine the indoor concentration of outdoor-sourced pollution for different housing typologies and how the results can be mapped using building stock models and Geographical Information Systems software to demonstrate the modifying effect of dwellings on occupant exposure to PM2.5 across London. Building archetypes broadly representative of those in the Greater London Authority were simulated for pollution infiltration using EnergyPlus. In addition, the influence of occupant behavior on indoor levels of PM2.5 from outdoor sources was examined using a temperature-dependent window-opening scenario. Results demonstrate a range of I/O ratios of PM2.5 , with detached and semi-detached dwellings most vulnerable to high levels of infiltration. When the results are mapped, central London shows lower I/O ratios of PM2.5 compared with outer London, an apparent inversion of exposure most likely caused by the prevalence of flats rather than detached or semi-detached properties. PRACTICAL IMPLICATIONS: Population exposure to air pollution is typically evaluated using the outdoor concentration of pollutants and does not account for the fact that people in London spend over 80% of their time indoors. In this article, building simulation is used to model the infiltration of outdoor PM2.5 into the domestic indoor environment for dwellings in a London building stock model, and the results mapped. The results show the variation in relative vulnerability of dwellings to pollution infiltration, as well as an estimated absolute indoor concentration across the Greater London Authority (GLA) scaled by local outdoor levels. The practical application of this work is a better understanding of the modifying effect of the building geometry and envelope design on pollution exposure, and how the London building stock may alter exposure. The results will be used to inform population exposure to PM2.5 in future environmental epidemiological studies.