Modified Kishner-Wolff reduction of 16α,17α-epoxy-l6β-methyl-Δ⁵-pregnene 3β-o1-20-one (Ⅱb) afforded a mirture of two 16β-methyl-Δ^5.17(20)-pregnadien-3β,16α-diols Ⅳa+Ⅳb geometrically isomeric at C_17-20. The structures of those compounds were proved by hydrogenation to compound Ⅴ, dehydration to compound Ⅵa, oxidation to compounds Ⅶa and Ⅶb and ozonization to yield acetaldehyde.