Catalytic hydrogenation of 5α-cholestan-3-one was investigated to examine the factors influencing the selective formation of the axial 3α-ol and it has been found that the most satisfactory yield of 3α-ol is realized using Urushibara nickel A, the nickel catalyst treated by acid, in hydrocarbon solvents at lower temperatures under high pressure. Preparation of epicholestanol and epicholesterol by this method is described.