Photosynthesis is commonly stimulated in grasslands with experimental increases in atmospheric CO2 concentration ([CO2]), a physiological response that could significantly alter the future carbon cycle if it persists in the long term. Yet an acclimation of photosynthetic capacity suggested by theoretical models and short-term experiments could completely remove this effect of CO2. Perennial ryegrass (Lolium perenne L. cv. Bastion) was grown under an elevated [CO2] of 600 µmol mol−1 for 10 years using Free Air CO2Enrichment (FACE), with two contrasting nitrogen levels and abrupt changes in the source : sink ratio following periodic harvests. More than 3000 measurements characterized the response of leaf photosynthesis and stomatal conductance to elevated [CO2] across each growing season for the duration of the experiment. Over the 10 years as a whole, growth at elevated [CO2] resulted in a 43% higher rate of light-saturated leaf photosynthesis and a 36% increase in daily integral of leaf CO2 uptake. Photosynthetic stimulation was maintained despite a 30% decrease in stomatal conductance and significant decreases in both the apparent, maximum carboxylation velocity (Vc,max) and the maximum rate of electron transport (Jmax). Immediately prior to the periodic (every 4–8 weeks) cuts of the L. perenne stands, Vc,max and Jmax, were significantly lower in elevated than in ambient [CO2] in the low-nitrogen treatment. This difference was smaller after the cut, suggesting a dependence upon the balance between the sources and sinks for carbon. In contrast with theoretical expectations and the results of shorter duration experiments, the present results provide no significant change in photosynthetic stimulation across a 10-year period, nor greater acclimation in Vc,max and Jmax in the later years in either nitrogen treatment.