The dispersion of airborne pollutants in the urban atmosphere is a complex, canopy-driven process. The intricate structure of the city, the high number of potential sources, and the large spatial domain make it difficult to predict dispersion patterns, to simulate a great number of scenarios, and to identify the high-impact emission areas. Here we show that these complex transport dynamics can be efficiently characterized by adopting a complex network approach. The urban canopy layer is represented as a complex network. Street canyons and their intersections shape the spatial structure of the network. The direction and the transport capacity of the flow in the streets define the direction and the weight of the links. Within this perspective, pollutant contamination from a source is modeled as a spreading process on a network, and the most dangerous areas in a city are identified as the best spreading nodes. To this aim, we derive a centrality metric tailored to mass transport in flow networks. By means of the proposed approach, vulnerability maps of cities are rapidly depicted, revealing the nontrivial relation between urban topology, transport capacity of the street canyons, and forcing of the external wind. The network formalism provides promising insight in the comprehensive analysis of the fragility of cities to air pollution.