The Grignard reaction of 11 beta-hydroxy-3,3-(ethylenedioxy)-pregn-5-en-20-one (1) affords both epimers (20R) (2) and (20S) (3) of the hydroxy derivative. The configuration R at C20 is established for the predominant epimer by the determination of the X-ray structure of the deketalized analog 4. C27H36O3, M(r)=408.58, orthorhombic, P2(1)2(1)2(1), a = 30.009(11), b = 6.323(1), c = 12.182(9)Angstrom, V = 2312(2)Angstrom(3), Z=4,D-x=1.17 g.cm(-3), CuK alpha radiation (lambda = 1.5418 Angstrom). The final R indice is 0.079 for 2058 observed reflections.