To efficiently obtain a high-purity labeled steroid from an obtainable general-purpose compound as a raw material useful for elucidating an organism function, etc., in a high yield by catalytically deuterating or catalytically tritiating a specific compound prepared by a reaction under prescribed conditions.

A compound of formula I [St is a steroid skeleton; R is H or a lower alkyl; X and Y are each H or a (protected) hydroxyl group] is oxidized to give a compound of formula II. The obtained compound of formula II is dehydrated to give a compound of formula III. The prepared compound is catalytically deuterated or catalytically tritiated to give a labeled steroid of formula IV (Z is deuterium or tritium). The compound of formula III the compound of formula IV and a compound of formula V [W1 and W2 are each a (protected)hydroxyl group] are new.