Tropospheric ozone (O3) and other pollutants significantly affect Chile's Metropolitan Region, posing risks to human health. As a secondary pollutant and a major photochemical oxidant, O3 formation is driven by anthropogenic volatile organic compounds (AVOCs) from the residential and transport sectors, the main sources of gaseous emissions. This study evaluated the AVOC capture capacity of leaf material from two tree species, Quillaja saponaria (native species) and Robinia pseudoacacia (exotic species), as potential urban biomonitors. Leaf samples were collected near nine SINCA official monitoring stations and the Antumapu University Campus, stored frozen, and analyzed by HS-SPME-GC/MSD for AVOC quantification. Photochemical reactivity and O3 formation potential were assessed using equivalent propylene concentration (Prop-Equiv) and Ozone Formation Potential (OFP) methods. The results showed that both species captured atmospheric AVOCs, confirming their role as bioindicators. However, Q. saponaria adsorbed significantly higher AVOC concentrations and exhibited greater tropospheric O3 formation potential than R. pseudoacacia. Given the AVOC adsorption capacity of both tree species, they could be used as biomonitors for styrene and also as a biomonitor for toluene in the case of Q. saponaria. This research highlights the importance of selecting tree capacity to improve urban air quality.