This study assessed leaf fluxes of CO2, CH4 and biogenic volatile organic compounds (BVOC) for two common urban tree species, Platanus × acerifolia (exotic) and Schinus molle (native), widely distributed in Santiago, Chile. The emission factors (EF) and the Photochemical Ozone Creation Index (POCI) for S. molle and P. × acerifolia were estimated. The global EF was 6.4 times higher for P. × acerifolia compared with S. molle, with similar rates of photosynthesis for both species. Isoprene represented more than 86% of the total BVOCs leaf fluxes being 7.6 times greater for P. × acerifolia than S. molle. For P. × acerifolia, BVOCs represented 2% of total carbon fixation while representing 0.24% for S. molle. These results may suggest that plant species growing outside their ecological range may exhibit greater BVOCs leaf fluxes, proportional to photosynthesis, compared to well-adapted ones. The results found may contribute to better urban forest planning.