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.