Understanding the processes that affect the triple oxygen isotope composition of atmospheric CO2during gas exchange can help constrain the interaction and fluxes between the atmosphere and the biosphere. We conducted leaf cuvette experiments under controlled conditions using three plant species. The experiments were conducted at two different light intensities and using CO2with different δ17O. We directly quantify the effect of photosynthesis on δ17O of atmospheric CO2for the first time. Our results demonstrate the established theory for δ18O is applicable to δ17O.CO2/at leaf level, and we confirm that the following two key factors determine the effect of photosynthetic gas exchange on the δ17O of atmospheric CO2. The relative difference between δ17O of the CO2entering the leaf and the CO2in equilibrium with leaf water and the back-diffusion flux of CO2from the leaf to the atmosphere, which can be quantified by the cm=ca ratio, where ca is the CO2mole fraction in the surrounding air and cm is the one at the site of oxygen isotope exchange between CO2and H2O. At low cm=ca ratios the discrimination is governed mainly by diffusion into the leaf, and at high cm=ca ratios it is governed by back-diffusion of CO2that has equilibrated with the leaf water. Plants with a higher cm=ca ratio modify the 117O of atmospheric CO2more strongly than plants with a lower cm=ca ratio. Based on the leaf cuvette experiments, the global value for discrimination against δ17O of atmospheric CO2during photosynthetic gas exchange is estimated to be-0:57±0:14% using cm=ca values of 0.3 and 0.7 for C4and C3plants, respectively. The main uncertainties in this global estimate arise from variation in cm=ca ratios among plants and growth conditions.