Polycyclic aromatic hydrocarbons (PAHs) produced by numerous anthropogenic activities are ubiquitous in the environment and have become a priority concern due to their potential severe biological impacts. A better understanding of PAH transfer at the catchment scale is therefore necessary to improve the management of PAH contaminants and protect rivers. Furthermore, the impact of changes in hydrological regimes and land uses on PAH fluxes should be specifically investigated. Accordingly, the current research monitors the contamination in atmospheric fallout, soils and rivers in a 950-km2 catchment (Orge River) characterized by an increasing urban gradient in downstream direction. During an entire hydrological year, river water contamination was quantified through regular sampling of both particulate and dissolved material at four river-monitoring stations, reflecting the increasing urbanization gradient. The significant input of PAHs from urban areas in downstream river sections corresponded to a specific PAH flux that reached 23 g km−2 y−1 despite the low sediment yield. Moreover, the comparison with runoff-specific fluxes reported in the literature underlined the major impact of urban runoff on the Orge River water and sediment quality. Nevertheless, the annual PAH load exported by the river (21 kg y−1) remained lower than the PAH inputs from atmospheric fallout (173 kg y−1), demonstrating the continuous accumulation of PAH from atmospheric fallout in the catchment soils. Consequently, the notably large PAH stock (close to 1000 tons) resulting from historical contamination of this early-industrialized region continues to increase due to ongoing atmospheric inputs.