Photophysical studies of pseudo-p-distyryl[2.2]paracyclophane, a model molecule of a stilbene dimer arranged in a brick-wall geometry, in tetrahydrofurane solution indicate the existence of at least two conformers in the ground state. The conformer A with the smallest optical gap of 3 eV has a short radiative lifetime of 3.3 ns, while the conformer B with an optical gap about 0.3 eV larger is much more abundant in solution and its radiative lifetime is about 10 times longer. Ab initio calculations show that the ground-state energy has a shallow minimum with respect to the torsional angle between the styryl side group and the paracyclophane core around the zero position, with the lowest energy conformation at a torsional angle of -21degrees. On this basis, A and B are assigned to flat and twisted conformations, respectively. Conformer B shows a partial decay of excited-state absorption and fluorescence with a time constant ranging from 5 to 30 ps, depending on excitation photon energy. We attribute this to isomerization of the stilbene moiety, which initially keeps conjugation in the ground state. The isomerization product is long-lived and tends to accumulate in solution.