The initial steps in the thermal decomposition of 2,5-dimethylfuran are identified as scission of the C-H bond in the methyl side chain and formation of beta- and alpha-carbenes via 3,2-H and 2,3-methyl shifts, respectively. A variety of channels are explored which prise the aromatic ring open and lead to a number of intermediates whose basic properties are essentially unknown. Once the furan ring is opened demethylation to yield highly unsaturated species such as allenylketenes appears to be a feature of this chemistry. The energetics of H abstraction by the hydroxyl radical (and other abstracting species) from a number of mono- and disubstituted methyl furans has been studied. H-atom addition to 2,5-dimethylfuran followed by methyl elimination is shown to be the most important route to formation of the less reactive 2-methylfuran. Identification of 2-ethenylfuran as an C(6)H(6)O intermediate in 2,5dimethylfuran flames is probably not correct and is more likely the isomeric 2,5-dimethylene-2,5-dihydrofuran for which credible formation channels exist.