Two conformations, 1 and 2, of pentaphenylethane are compared. The ground state conformation 2 results from an earlier computational work by force fields procedures [1], whereas 1 has been more recently observed in the crystalline state by X‐ray diffraction methods. The strain energy of 1 minimizes very close to the value computed for 2. These conformations belong to two distinct minima of the potential energy surface and are at the most separated by a barrier of about 7 kcal/mol. The pathway converting 1 into its enantiomer is shown to run over a barrier of only 1.5 kcal/mol.