The pyrolyses of anisole (C6H5OCH3), d(3)-anisole (C6HSOCD3), and d(8)-anisole (C6D5OCD3) have been studied using a hyperthermal tubular reactor and photoionization reflectron time-of-flight mass spectrometer. Gas exiting the reactor is subject to an immediate supersonic expansion after a residence time of approximately 65 mu s. This allows the detection of highly reactive radical intermediates. Our results confirm that the first steps in the thermal decomposition of anisole are the loss of a methyl group to form phenoxy radical, followed by ejection of a CO to form cyclopentadienyl radical (c-C5H5); C6H5OCH3 -> C6HSO + CH3; C6HSO -> c-C5H5 + CO. At high temperatures (T-wall = 1200 degrees C - 1300 degrees C) the c-C5H5 decomposes to propargyl radical (CH2CCH) and acetylene; c-C5H5 -> CH2CCH + C2H2. The formation of benzene and naphthalene is demonstrated with 1 + 1 resonance-enhanced multiphoton ionization. Propargyl radical recombination is a significant benzene formation channel. However, we show the majority of benzene is formed by a ring expansion reaction of methylcyclopentadiene (C5H5CH3) resulting from methyl radical addition to cyclopentadienyl radical; CH3 + c-C5H5 -> C5H5CH3 -> C6H6 + 2H. The naphthalene is generated from cyclopentadienyl radical recombination; 2c-C5H5 -> C5H5-C5H5 -> C10H8 + 2H. The respective intermediate amu 79 and 129 species associated with these reactions are detected, confirming the stepwise nature of the decompositions. These reactions are verified by pyrolysis studies of cyclopentadiene (C5H6) and C5H5CH3 obtained from rapid thermal dissociation of the respective dimer compounds, as well as pyrolysis studies of propargyl bromide (BrCH2CCH).