Onion (Allium cepa L.) plants were examined to determine the photosynthetic role of CO2 that accumulates within their leaf cavities. Leaf cavity CO2 concentrations ranged from 2250 μL L(-1) near the leaf base to below atmospheric (<350 μL L(-1)) near the leaf tip at midday. There was a daily fluctuation in the leaf cavity CO2 concentrations with minimum values near midday and maximum values at night. Conductance to CO2 from the leaf cavity ranged from 24 to 202 μmol m(-2) s(-1) and was even lower for membranes of bulb scales. The capacity for onion leaves to recycle leaf cavity CO2 was poor, only 0.2 to 2.2% of leaf photosynthesis based either on measured CO2 concentrations and conductance values or as measured directly by (14)CO2 labeling experiments. The photosynthetic responses to CO2 and O2 were measured to determine whether onion leaves exhibited a typical C3-type response. A linear increase in CO2 uptake was observed in intact leaves up to 315 μL L(-1) of external CO2 and, at this external CO2 concentration, uptake was inhibited 35.4±0.9% by 210 mL L(-1) O2 compared to 20 mL L(-1) O2. Scanning electron micrographs of the leaf cavity wall revealed degenerated tissue covered by a membrane. Onion leaf cavity membranes apparently are highly impermeable to CO2 and greatly restrict the refixation of leaf cavity CO2 by photosynthetic tissue.