I am often reminded of the famous saying of Goethe: "Vedi Napoli e poi muori! - See Naples and die!". Sadly, Naples is now confronted with a number of serious, ongoing problems with a need to alleviate pressure on the worsening environment. One serious problem facing the environment is the presence of the potentially hazardous persistent organic pollutants (POPs), although few systematic studies at regional scale have been conducted. In this study, samples of soil, air, and bulk deposition were collected in Naples metropolitan area (NMA) to characterize the status of POPs, including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). The results obtained showed that most of these compounds are pervasive in all the studied environmental matrices, especially in some hotspot areas, such as the Bagnoli Brownfield Site and the infamous "Triangle of the Death", where unwanted ecological risk conditions for PAHs and Endosulfan were determined, respectively. The interactional complexity between urban and the surrounding rural areas was also confirmed, as is the role that urban areas play in the migration and transformation process of POPs. High urban-rural gradients for atmospheric PAHs and PCBs were observed in the NMA, and the urban areas were identified as the emission source of these contaminants. Similarly, the OCP residues, historically originated from the nearby agricultural regions, experience long-term soil re-emission and continuously influence the connected urban environment via atmospheric transport processes.