Two campaigns were conducted in 2003 and 2004 at sites of different characteristics in São Paulo State. Atmospheric samples were collected twice a month during a 1-year campaign (an extensive campaign) from April 2003 to May 2004 at São Paulo City (SPA) site.The results showed that the pollutant concentrations were controlled not only by local source emissions but also through pollutant transport, both of which were dictated by the prevailing meteorological conditions. Chrysene, benzo(e)pyrene, and benzo(b)fluoranthene were the major compounds found, and diagnostic ratios indicated the multiplicity of sources: industrial, vehicular emission, and atmospheric transport. Intensive campaign (from July 15 to 30, 2003) samples showed higher cancer risk than those collected in the extensive campaign. Samples collected at the urban site (SPA) presented comparable values of PM 10 to the urban site influenced by sugarcane burning (Araraquara, ARQ). On the other hand, PAH average concentrations were higher at SPA than at other sites. In both campaigns, the highest value for dry atmospheric deposition flux was found in autumn and winter. Individually, BPe presented the highest deposition flux followed by BbF in the intensive campaign. It seems that during those periods, the dry deposition was the main airborne PAH removal mechanism. Diagnostic ratios suggested also vehicular emissions at the sites and photochemical reactions influencing in the atmospheric particulate matter composition. SPA and PRB samples presented higher cancer risk than ARQ in the intensive campaign.