At present, an in-depth knowledge of polycyclic aromatic hydrocarbons (PAHs) in the multimedia system of the urban environment remains limited. Taking the Naples metropolitan area (NMA) for instance, we simulated the cross-media transfer of PAHs using a multimedia urban model, involving air, water, soil, sediment, vegetation, and impervious film. The results indicated that the predicted PAH values in 2015 match well with their corresponding in-situ monitoring data. The PAH emission inventory and the simulated mass in various media all showed a downward trend from 2015 to 2020 due to national energy conservation policies and Corona Virus Disease 2019. The simulated mass of PAHs in the soil and sediment phases was 896.8 and 232.7 kg in 2020, respectively, contributing together to 96.7% of PAHs in the NMA. And they were identified as the greatest sinks for PAHs, and exhibited the longest retention duration, with values of PAH persistence reaching approximately 548.8 – 2,0642.3 hours. The results of transfer fluxes indicated that local emissions and atmospheric advection were the primary routes affecting the distribution of PAHs. The sensitivity analysis indicated that atmospheric advection rate was the most critical parameter for air, soil, vegetation, and film, whereas water concentration and sediment degradation rate were vital for water and sediment, respectively. This study offered valuable insights into how human activity contributes to the status and fate of PAHs in the urban environment.