The anticipated climate change during the next decades is posing crucial challenges to ecosystems. In order to decrease the vulnerability of forests, introducing tree species’ mixtures are a viable strategy, with deep-rooting native Silver fir (Abies alba) being a primary candidate for admixture into current pure stands of European beech (Fagus sylvatica) especially in mountainous areas. Such a change in forest structure also has effects on the regional scale, which, however, have been seldomly quantified. Therefore, we measured and modeled radiative balance and air chemistry impacts of admixing Silver fir to European beech stands, including changes in biogenic volatile organic compound emissions. An increased fraction of Silver fir caused a smaller albedo and a (simulated) larger evapotranspiration, leading to a dryer and warmer forest. While isoprene emission was negligible for both species, sesquiterpene and monoterpene emissions were larger for fir than for beech. From these differences, we derived that ozone concentration as well as secondary organic aerosols and cloud condensation nuclei would increase regionally. Overall, we demonstrated that even a relatively mild scenario of tree species change will alter the energy balance and air quality in a way that could potentially influence the climate on a landscape scale.