Understanding air pollution in urban areas is crucial to identify mitigation actions that may improve air quality and, consequently, minimize human exposure to air pollutants and their impact. This study aimed to assess the temporal evolution of the air quality in the city of Setúbal (Portugal) during a time period of 10 years (2003–2012), by evaluating seasonal trends of air pollutants (PM10, PM2.5, O3, NO, NO2 and NOx) measured in nine monitoring stations. In order to identify emission sources of particulate matter, PM2.5 and PM2.5–10 were characterized in two different areas (urban traffic and industrial) in winter and summer and, afterwards, source apportionment was performed by means of Positive Matrix Factorization. Overall, the air quality has been improving over the years with a decreasing trend of air pollutant concentration, with the exception of O3. Despite this improvement, levels of PM10, O3 and nitrogen oxides still do not fully comply with the requirements of European legislation, as well as with the guideline values of the World Health Organization (WHO). The main anthropogenic sources contributing to local PM levels were traffic, industry and wood burning, which should be addressed by specific mitigation measures in order to minimize their impact on the local air quality.