, the concentrations and chemical composition of PM 2.5 and PM 2.5-10 (particulate matter with a diameter of 2.5 μm or less and between 2.5 and 10 μm, respectively) were monitored at four sampling points in the Rio de Janeiro metropolitan area, and two of the points were in close proximity to the 2016 Olympic Games facilities with a total of 122 samples at each sampling point. At all four sampling stations, the annual mean value of PM 10 was above the World Health Organization (WHO) air quality guideline, although frequent violations of the 24 h guideline were observed at only two of the points, Duque de Caxias and Taquara. On the other hand, PM 2.5 concentrations at the four sampling points met both the annual and 24 h WHO PM 2.5 air quality guidelines. The vehicular contribution to PM 2.5 ranged from 48 to 70%, with a mean value of 59 ± 9%. Considering that the Brazilian market already has fuel quality that is comparable to international standards (gasoline S50 and diesel S10), further air quality improvements are expected with investments in a public transport network, urban mobility programs and fleet renewal, which are considered a legacy of the 2016 Olympic Games.