Leaf and woody plant tissue (<I>Pinus ponderosa</I>, <I>Eucalyptus saligna</I>, <I>Quercus gambelli</I>, <I>Saccharum officinarum</I> and <I>Oriza sativa</I>) were heated from 30 to 300°C and volatile organic compound (VOC) emissions were identified and quantified. Major VOC emissions were mostly oxygenated and included acetic acid, furylaldehyde, acetol, pyrazine, terpenes, 2,3-butadione, phenol and methanol, as well as smaller emissions of furan, acetone, acetaldehyde, acetonitrile and benzaldehyde. Total VOC emissions from distillation and pyrolysis were on the order of 10 gC/kgC dry weight of vegetation, as much as 33% and 44% of CO<sub>2</sub> emissions (gC(VOC)/gC(CO<sub>2</sub>)) measured during the same experiments, in air and nitrogen atmospheres, respectively. <P style="line-height: 20px;"> The emissions are similar in identity and quantity to those from smoldering combustion of woody tissue and of different character than those evolved during flaming combustion. VOC emissions from the distillation of pools and endothermic pyrolysis under low turbulence conditions may produce flammable concentrations near leaves and may facilitate the propagation of wildfires. VOC emissions from charcoal production are also related to distillation and pyrolysis; the emissions of the highly reactive VOCs from production are as large as the carbon monoxide emissions.