The Greater Bay Area (GBA) of China is experiencing a high level of exposure to outdoor PM2.5 pollution. The variations in the exposure level are determined by spatiotemporal variations in the PM2.5 concentration and population. To better guide public policies that aim to reduce the population exposure level, it is essential to explicitly decompose and assess the impacts of different factors. This study took advantage of high-resolution satellite observations to characterize the long-term variations in population exposure to outdoor PM2.5 for cities in the GBA region during the three most-recent Five-Year Plan (FYP) periods (2001–2015). A new decomposition method was then used to assess the impact of PM2.5 variations and demographic changes on the exposure variation. Within the decomposition framework, an index of pollution-population-coincidence–induced PM2.5 exposure (PPCE) was introduced to characterize the interaction of PM2.5 and the population distribution. The results showed that the 15-year average PPCE levels in all cities were positive (e.g., 6 µg/m3 in Guangzhou), suggesting that unfavorable city planning had led to people dwelling in polluted areas. An analyses of the spatial differences in PM2.5 changes showed that urban areas experienced a greater decrease in PM2.5 concentration than did rural areas in most cities during the 11th (2006–2010) and 12th (2011–2015) FYP periods. These spatial differences in PM2.5 changes reduced the PPCE levels of these cities and thus reduced the exposure levels (by as much as -0.58 µg/m3/year). The population migration resulting from rapid urbanization, however, increased the PPCE and exposure levels (by as much as 0.18 µg/m3/year) in most cities during the three FYP periods considered. Dongguan was a special case in that the demographic change reduced the exposure level because of its rapid development of residential areas in cleaner regions adjacent to Shenzhen. The exposure levels in all cities remained high because of the high mean PM2.5 concentrations and their positive PPCE. To better protect public health, control efforts should target densely populated areas and city planning should locate more people in cleaner areas.