The synthesis, crystallization, single crystal X-ray structure, and solid state dynamics of molecular rotor 3 provided with a high symmetry order and relatively cylindrical bicyclo[2.2.2]octane (BCO) rotator linked to mestranol fragments were investigated in this work. By use of solid state C-13 NMR, three rotating fragments were identified within the molecule: the BCO, the C19 methoxy and the C18 methyl groups. To determine the dynamics of the BCO group in crystals of 3 by variable temperature H-1 spin-lattice relaxation (VT H-1 T-1), we determined the H-1 T-1 contributions from the methoxy-deuterated isotopologue rotor 3-d(6). The contributions from the quaternary methyl group C18 were estimated by considering the differences between the VT H-1 T-1 of mestranol 8 and methoxy-deuterated mestranol 8-d(3). From these studies it was determined that the BCO rotator in 3 has an activation energy of only 1.15 kcal mol(-1), with a barrier for site exchange that is smaller than those of methyl (E-a = 1.35 kcal mol(-1)) and methoxy groups (E-a = 1.92 kcal mol(-1)), despite their smaller moments of inertia and surface areas.