Industrial development from the second half of the 20th century coupled with population growth and concentration in urban areas has accentuated the concern for potential effects and impacts from air pollutant emissions on environmental and human health. This study examined the Estarreja region, an urban area that has one of the largest chemical complexes in Portugal, a complex that was recently under expansion. In the scope of the INSPIRAR project, individual daily exposure of a group of individuals to particulate matter of 10 μm aerodynamic diameter (PM10) and nitrogen dioxide (NO2) in two phases was determined using a microenvironmental approach. In this context, personal daily activity profiles of individuals were established for their normal routine by personal interviews. These profiles enabled determination of where each individual was at each moment of the day. Utilizing this information with hourly air quality maps simulated with URBAIR air quality model and indoor/outdoor relationships, it was possible to calculate personal daily exposure of each individual to air pollutants. Results from the analysis of daily activity profiles showed a high level of sedentariness of this population and long durations spent indoors. The studied individuals displayed high personal PM10 and NO2 exposure variability. Data demonstrated possible error when a single concentration measurement was assumed as a proxy of exposure. In general, no significant differences were found between the two population groups, indicating that workers of the chemical complex were not exposed to a greater extent to PM10 and NO2 than the general population working in the same area.