The radical cation of Dewar benzene, 1(center dot+), has been generated and observed by optical spectroscopy in cryogenic matrices. 1(center dot+) distinguishes itself by a charge resonance band at 600 nm, very similar in shape and position to that observed for the related radical cation of norbornadiene. This coincidence indicates that in ground-state 1(center dot+) the odd electron is also located in a pi-MO. The energy of the charge resonance transition, which is very sensitive to the dihedral angle between the four-membered rings in 1(center dot+), is predicted consistently too low by TD-DFT and CASPT2. Probably this angle is too large in the B3LYP and CASSCF geometries. As 1(center dot+) can be observed at 77 K, it must be separated by a barrier of at least 7-8 kcal/mol from its very exothermic decay to the radical cation of benzene, 2(center dot+). An analysis shows that the ring-opening of 1(center dot+) is a multistep proccess involving two avoided crossings between potential surfaces of different symmetry and electronic nature. Owing to the orbital symmetry-forbidden nature of the process, the energy of 1(center dot+) starts by increasing steeply on stretching the central C-C bond, but then the system undergoes a crossing to a (2)A(1) surface which leads adiabatically to an excited state of 2(center dot+). Therefore, another avoided crossing must be transited before the molecule can decay on the ground-state surface of 2(center dot+). The rearrangement of 1(center dot+) to 2(center dot+) is an example of a "pseudodiabatic" thermal reaction that transits between potential surfaces representing very different electronic structures.