The fuel matrix used in Brazil is unique around the world. The intensive use of hydrated ethanol, gasohol (gasoline with 25% v/v of ethanol), compressed natural gas (CNG), and biodiesel leads to a peculiar composition of the urban atmosphere. From 1998 to 2002 an increase in formaldehyde levels was observed and since then, a reduction. This work presents a monitoring campaign that was executed from March 2004 to February 2009 by sampling at early morning on every sunny Wednesday for a total of 183 samples. The results indicate a strong reduction in formaldehyde levels from 2004 (average of 135.8μgm−3 with SD 28.4μgm−3) to 2009 (average of 49.3μgm−3 with SD 27.4μgm−3). The levels of acetaldehyde showed a slight reduction from 2004 (average of 34.9μgm−3 with SD 8.0μgm−3) to 2009 (average of 26.8μgm−3 with SD 11.5μgm−3). Comparing the results with the concurrent evolution of the fleet and of fuel composition indicates that the observed formaldehyde levels could be associated with the increase in ethanol use and in CNG use by engines with improved technology over the first converted CNG engines. Modelling studies using the OZIPR trajectory model and the SAPRC chemical mechanism indicate that formaldehyde is the main ozone precursor in Rio de Janeiro and acetaldehyde is the forth one.