Efficient enantioselective isomerizations of prochiral allylic alcohols have been independently reported by our group and others in recent years. However, diastereoselective isomerization with chiral substrates had been barely documented. Herein, we have first conducted catalyst-directed diastereoselective isomerization with enantioenriched allylic alcohols using both enantiomers of catalyst. Good yields, perfect dr and excellent ee were commonly obtained. Later, we evaluated steroidal allylic alcohols in the catalyst-directed diastereoselective isomerization for the stereocontrolled installation of C20, the first tertiary stereocenter of the acyclic domain in steroid derivatives. Following a uniform yet modular synthetic route to prepare a variety of steroidal allylic alcohols, a range of allylic alcohols were employed in the diastereoselective isomerization. (R)-Catalyst provided indifferently access to the natural C20-(R) and unnatural C20-(S) configurations. The scope of our method was further highlighted through structural diversification in the side chain and within the polycyclic domain of advanced and complex steroidal architectures.