The structure of cholest-5-en-3-yl 4-vinylbenzoate, C36H52O2, was determined by X-ray diffraction. The molecule is extended along the b axis, with the benzoate group orientated out of the plane of the tetracyclic core by 48.1(1)degrees. The molecules are packed in an antiparallel manner. The packing of antiparallel pairs of molecules in the unit cell is correlated to two types of interactions that coexist in the liquid-crystalline phase of cholesterol based cyclic siloxane macromolecules.