Soil, street dust, and bulk deposition (dry and wet deposition) were collected in the Metropolitan Area of Buenos Aires (MABA), Argentina, to assess the polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) pollution and the potential risks to human health. Compared with other countries, the mean concentration of PAHs and PCBs in surface soils, street dust and bulk deposition of MABA were at a low or moderate level. Average PAHs and PCBs concentrations in bulk deposition (5.7 ± 5.1 and 0.41 ± 0.25 µg g−1, respectively) were five and ten times higher than those of soil (1.08 ± 0.98 and 0.02 ± 0.01 µg g−1) and street dust (1.2 ± 0.95 and 0.04 ± 0.03 µg g−1), respectively. Different compositional profiles, observed in the three matrices for both groups of contaminants, could be attributed to dissimilar source contribution, partition processes between gas and particulate phases, and transformation. The most contaminated bulk deposition presented higher values for cancer and non-cancer risks relative to soil and street dust. In all matrices, non-carcinogenic risks were below the safety threshold (HI < 1). Regarding carcinogenic risks, exposure to both bulk deposition and soil indicated a moderated potential for cancerous development (Incremental lifetime cancer risk ~ 3.0 × 10−6).