Trees are considered to be an effective tool for metal pollution biomonitoring. In the present study, the concentration of metals (Cu, Pb, Zn, Cd, Co, Ni, Fe, Mn, and Al) in black poplar leaves (Populus nigra L.), together with the concentration of PM10, PM2.5, PM1, and total suspended particles (TSP), was used for the air pollution biomonitoring in 12 sites from various areas of Cluj-Napoca city, Romania. The concentration of PM10 in the air was high, but their metal content was low. However, Cu, Pb, and Zn were moderately enriched, while Cd was highly enriched in PM10 due to anthropogenic sources. The average metal concentration in leaves decreased in the order Zn>>Fe>Mn>Al>Pb>Ni>Cu>Co>Cd and increased with the increase of PM10 concentration, indicating that poplar leaves are sensitive to air pollution. The principal component analysis indicated that traffic, waste burning, road dust resuspension, and soil contamination are the main anthropogenic sources of metals in poplar leaves. The results indicated that black poplar leaves are a suitable biomonitoring tool for metal pollution, in urban environments.