The photodissociation of isotope-labeled toluene C(6)H(5)CD(3) and C(6)H(5)(13)CH(3) molecules at 6.4 eV under collision-free conditions was studied in separate experiments by multimass ion imaging techniques. In addition to the major dissociation channels, C(6)H(5)CD(3) --> C(6)H(5)CD(2) + D and C(6)H(5)CD(3) --> C(6)H(5) + CD(3), the respective photofragments CD(2)H, CDH(2), and CH(3) and their heavy fragment partners C(6)H(4)D, C(6)H(3)D(2), and C(6)H(2)D(3) were observed from C(6)H(5)CD(3) dissociation. Photofragments (13)CH(3) and CH(3), and their heavy fragment partners C(6)H(5) and (13)CC(5)H(5), were also observed from C(6)H(5)(13)CH(3) dissociation. Our results show that 25% of the excited toluene isomerizes to a seven-membered ring (cycloheptatriene) and then rearomatizes prior to dissociation. The isomerization pathway competes with direct C-C bond and C-H bond dissociation. The significance of this isomerization is that the carbon atoms and hydrogen atoms belonging to the alkyl group are involved in an exchange with those atoms in the aromatic ring during isomerization. The dissociation rate of toluene at 193 nm is measured to be (1.17 +/- 0.1) x 10(6) s(-)(1).