Leaf structure and chemistry both play critical roles in regulating photosynthesis. Yet, a key unresolved issue in climate change research is the role of changes in leaf structure in photosynthetic responses to temperature and atmospheric CO2 concentration ([CO2]), ranging from pre-industrial to future levels. We examined the interactive effects of [CO2] (290, 400 and 650μLL-1) and temperature (ambient, ambient +4°C) on leaf structural and chemical traits that regulate photosynthesis in Eucalyptus sideroxylon A.Cunn. ex Woolls. Rising [CO2] from pre-industrial to elevated levels increased light-saturated net photosynthetic rates (Asat), but reduced photosynthetic capacity (Amax). Changes in leaf N per unit area (Narea) and the number of palisade layers accounted for 56 and 14% of the variation in Amax, respectively, associated with changes in leaf mass per area. Elevated temperature increased stomatal frequency, but did not affect Amax. Further, rising [CO2] and temperature generally did not interactively affect leaf structure or function. These results suggest that leaf Narea and the number of palisade layers are the key chemical and structural factors regulating photosynthetic capacity of E. sideroxylon under rising [CO2], whereas the lack of photosynthetic responses to elevated temperature may reflect the limited effect of temperature on leaf structure and chemistry.