The photochemistry of various mono- and dimethoxy-substituted α-bromoacetophenones has been investigated by laser flash photolysis in organic solvents. The short-lived excited singlet states cleave to yield bromine atoms and the corresponding methoxyphenacyl radicals with quantum yields ranging from 0.13 to 0.35. With the exception of 4-methoxy-α-bromoacetophenone (6), all other substrates yield readily detectable triplet states; these have π,π* character and are very poor hydrogen abstractors. Triplet decay does not contribute to methoxyphenacyl radical formation. While methoxyphenacyl radicals may have a spin density as high as 0.3 at the carbonyl oxygen, which accounts for the alkoxy-like visible band in their absorption spectrum, their chemical reactivity is dominated by the radical character at the carbon site. Methoxyphenacyl radicals are modest hydrogen abstractors; for example, reaction of6with 1,4-cyclohexadiene occurs with a rate constant of 2.6 × 105 M−1s−1, while for addition to the double bond in 1,1-diphenylethylene the rate constant is 9.4 × 107 M−1s−1. Additions to other double bonds are likely to be slower (e.g.,12 + 1,3-cyclohexadiene,k ≤ 105 M−1s−1). In contrast, reaction with oxygen occurs withkq = 2.5 × 109 M−1s−1. Under the conditions relevant for their participation in paper yellowing, the methoxyphenacyl radicals will be converted to peroxyl radicals. These probably play a key role in the oxidative photodegradation of lignin.Keywords: methoxyphenacyl radicals, α-bromoacetophenones, laser flash photolysis.