Production of C7H7+ from toluene molecular ion (TOL.+) was studied using mass-analyzed ion kinetic energy spectrometry. The kinetic energy release distribution (KERD) was determined, which showed Chat both benzylium (Bz(+)) and tropylium (Tr+) ions were produced from TOL.+. The Interconversion between the molecular ions of toluene and cycloheptatriene prior to the dissociations was confirmed. Ab initio calculations at the HF/6-31G** and G2(MP2,SVP) levels were carried out for some important chemical species. The KERD in the Bz(+) channel was calculated using the statistical phase space theory, while classical trajectory calculations were done to obtain the theoretical KERD in the Tr+ channel. The Tr+/Bz(+) branching ratio determined by analyzing the experimental KERD was much larger than reported previously.