Trees play a pivotal role in improving urban environmental quality and provide several ecosystem services including the removal of pollutants from the air, such as particular matter (PM) and potentially toxic elements (PTE). Therefore, understanding the tree PM and PTE capturing potential, also in connection with plant species, is of great concern, especially in urban areas. This study aims to reveal the link between the elemental composition of PM deposited on tree leaves and soils PTE contents, as well as to rank the PM capturing efficiency of 10 different tree species growing under the impact of urban environments. This also allowed us to test the efficiency of PM deposited on tree leaves as a PTE biomonitoring and pollution source identification tool, in the two biggest urban areas of Armenia. Indeed, high contents of PTE are detected in both soil- and leaf-deposited PM from sites characterized by the presence of localized and active pollution sources (i.e., industrial unites, high traffic, etc.), which are identified by specific tracers (such as Mo, Cu, Zn, Pb, and Cd). Among the studied tree species, the highest PM amount per unit leaf area is observed for Platanus orientalis, but elm species are also identified as promising canditates to be considered for their PM removing potential, and need to be included in future more details studies.