As a major source of air pollution, particulate matter (PM) and associated toxic trace elements pose potentially serious threats to human health and environmental safety. As is known that plants can reduce air PM pollution. However, the relationship between PM of different sizes and toxic trace elements in foliar PM is still unclear. This study was performed to explore the association between PM of different sizes (PM2.5, PM10, PM>10) and toxic trace elements (As, Al, Cu, Zn, Cd, Fe, Pb) as well as the correlation among toxic trace elements of six roadside plant species (Cinnamomum camphora, Osmanthus fragrans, Magnolia grandiflora, Podocarpus macrophyllus, Loropetalum chinense var. rubrum and Pittosporum tobira) in Changsha, Hunan Province, China. Results showed that P. macrophyllus had the highest ability to retain PM, and C. camphora excelled in retaining PM2.5. The combination of P. macrophyllus and C. camphora was highly recommended to be planted in the subtropical city to effectively reduce PM. The toxic trace elements accumulated in foliar PM varied with plant species and PM size. Two-way ANOVA showed that most of the toxic trace elements were significantly influenced by plant species, PM size, and their interactions (P < 0.05). Additionally, linear regression and correlation analyses further demonstrated the homology of most toxic trace elements in foliar PM, i.e., confirming plants as predictors of PM sources as well as environmental monitoring. These findings contribute to urban air pollution control and landscape configuration optimization.