One procedure for the organic synthesis of trans-cycloheptene is by singlet photosensitization of cis-cycloheptene with methyl benzoate and ultraviolet light at −35 °C.

[2] Because the barrier for rotation of the double bond in ethylene is approximately 65 kcal/mol (270 kJ/mol) and can only be lowered by the estimated strain energy of 30 kcal/mol (125 kJ/mol) present in the trans-isomer, trans-cycloheptene should be a stable molecule just as its homologue trans-cyclooctene.

The trans-cycloheptene isomerization mechanism is not simple alkene-bond rotation, but rather an alternative lower energy pathway.

[2] Based on the experimentally observed second order reaction kinetics for isomerization, two trans-cycloheptene molecules in the proposed pathway first form a diradical dimer.

The two heptane radical rings then untwist to an unstrained conformation, and finally the dimer fragments back into two cis-cycloheptene molecules.