A comprehensive modelling approach has been developed to predict population exposure to the ambient air PM2.5 concentrations in different microenvironments in London. The modelling approach integrates air pollution dispersion and exposure assessment, including treatment of the locations and time activity of the population in three microenvironments, namely, residential, work and transport, based on national demographic information. The approach also includes differences between urban centre and suburban areas of London by taking account of the population movements and the infiltration of PM2.5 from outdoor to indoor. The approach is tested comprehensively by modelling ambient air concentrations of PM2.5 at street scale for the year 2008, including both regional and urban contributions. Model analysis of the exposure in the three microenvironments shows that most of the total exposure, 85%, occurred at home and work microenvironments and 15% in the transport microenvironment. However, the annual population weighted mean (PWM) concentrations of PM2.5 for London in transport microenvironments were almost twice as high (corresponding to 13-20 µg/m3) as those for home and work environments (7-12 µg/m3). Analysis has shown that the PWM PM2.5 concentrations in central London were almost 20% higher than in the surrounding suburban areas. Moreover, the population exposure in the central London per unit area was almost three times higher than that in suburban regions. The exposure resulting from all activities, including outdoor to indoor infiltration, was about 20% higher, when compared with the corresponding value obtained assuming inside home exposure for all times. The exposure assessment methodology used in this study predicted approximately over one quarter (-28%) lower population exposure, compared with using simply outdoor concentrations at residential locations. An important implication of this study is that for estimating population exposure, one needs to consider the population movements, and the infiltration of pollution from outdoors to indoors.