Recent work has suggested that the photosynthetic rate of certain C4 species can be stimulated by increasing CO2 concentration, [CO2], even under optimal water and nutrients. To determine the basis for the observed photosynthetic stimulation, we tested the hypothesis that the CO2 leak rate from the bundle sheath would be directly related to any observed stimulation in single leaf photosynthesis at double the current [CO2]. Three C4 species that differed in the reported degree of bundle sheath leakiness to CO2, Flaveria trinervia, Panicum miliaceum, and Panicum maximum, were grown for 31–48 days after sowing at a [CO2] of 350 μl l−1 (ambient) or 700 μl l−1 (elevated). Assimilation as a function of increasing [CO2] at high photosynthetic photon flux density (PPFD, 1 600 μmol m−2 s−1) indicated that leaf photosynthesis was not saturated under current ambient [CO2] for any of the three C4 species. Assimilation as a function of increasing PPFD also indicated that the response of leaf photosynthesis to elevated [CO2] was light dependent for all three C4 species. The stimulation of leaf photosynthesis at elevated [CO2] was not associated with previously published values of CO2 leak rates from the bundle sheath, changes in the ratio of activities of PEP-carboxylase to RuBP carboxylase/oxgenase, or any improvement in daytime leaf water potential for the species tested in this experiment. In spite of the simulation of leaf photosynthesis, a significant increase in growth at elevated [CO2] was only observed for one species, F. trinervia. Results from this study indicate that leaf photosynthetic rates of certain C4 species can respond directly to increased [CO2] under optimal growth conditions, but that the stimulation of whole plant growth at elevated carbon dioxide cannot be predicted solely on the response of individual leaves.