The products of an electrical discharge containing toluene are :interrogated.using resonance-enhanced multiphoton ionization and laser-induced fluorescence spectroscopies. A previously unreported electronic spectrum recorded at m/z = 105, with a putative origin band at 26053 cm(-1), is assigned to methyltropyl radical, which appears to be a major product of the toluene discharge, plausibly arising from CH insertion. All three o-, m-, and p-xylyl isomers are also identified. These isomers are detected in electrical discharges containing various xylenes, where it is also found that interconversion occurs: A discharge of o-xylene produces some m-xylyl; a discharge of m-xylene produces some oxylyl; and a discharge of p-xylene produces all three isomers. No alpha-amethylbenzyl was detected, but styrene was. These observations are supported by state-of-the-art quantum chemical calculations, which reveal an isomerization pathway between methyltropyl and xylyl radicals for which there is no analogue in the canonical tropyl benzyl isomerization.