The thermal isomerization of tricyclo[4.1.0.0(2,) (7)]heptene has been studied using computational chemistry with structures determined at the MCSCF level and energies at the MRMP2 level. Both the allowed conrotatory and forbidden disrotatory pathways have been elucidated resulting in cycloheptatriene isomers. Four reaction channels are available for the conrotatory pathway depending on which bond breaks first in the bicyclobutane moiety leading to enantiomeric pairs of (E,Z,Z)-1,3,5-cycloheptatriene and (Z,E,Z)-1,3,5-cycloheptatriene intermediates. The activation barrier is calculated to be 31.3 kcal.mol(-1) for two channels and 37.5 kcal.mol(-1) for the other two. The lower activation barrier leading to the (E,Z,Z)-1,3,5-cycloheptatriene enantiomeric pair is proposed to be due to resonance within the transition state. The same behavior was observed for the disrotatory pathway with activation barriers of 42.0 kcal.mol(-1) and 55.1 kcal.mol(-1) for the two channels, again with one transition state resonance stabilized. The barriers for trans double bond rotation of the intermediate cycloheptatrienes are determined to be 17.1 and 17.4 kcal.mol(-1), about 5 kcal.mol(-1) more than that for the seven carbon diene (E,Z)-1,3-cycloheptadiene. The electrocyclic ring closure of the trans cycloheptatrienes have been modeled and barriers determined to be 11.1 and 11.9 kcal.mol(-1) for the formation of bicyclo[3.2.0]hepta-2,6-diene. This structure was previously reported as the end product for thermolysis of the parent tricyclo[4.1.0.0(2, 7)]heptene. The thermodynamically more stable cycloheptatriene can be formed from bicyclo[3.2.0]hepta-2,6-diene through a two step process with a calculated pseudo first-order barrier of 36.4 kcal.mol(-1). The trans-cycloheptatrienes reported herein are the first characterization of a small seven-membered ring triene with a trans double bond.