Theoretical calculations, based on both the chemical and isotopic composition of sedimentary rocks, indicate that atmospheric O2 has varied appreciably over Phanerozoic time, with a notable excursion during the Permo-Carboniferous reaching levels as high as 35% O2. This agrees with measurements of the carbon isotopic composition of fossil plants together with experiments and calculations on the effect of O2 on photosynthetic carbon isotope fractionation. The principal cause of the excursion was the rise of large vascular land plants and the consequent increased global burial of organic matter. Higher levels of O2 are consistent with the presence of Permo-Carboniferous giant insects, and preliminary experiments indicate that insect body size can increase with elevated O2. Higher O2 also may have caused more extensive, possibly catastrophic, wildfires. To check this, realistic burning experiments are needed to examine the effects of elevated O2 on fire behavior.