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A method of producing 3-alkoxy-1, 3, 5(10)-triene-6-one-steroid derivatives having, in the steroid skeleton thereof, a partial structure of A- and B-rings represented by formula (2) : (wherein R represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aralkyl group), including reacting a 19-norsteroid derivative having, in the steroid skeleton thereof, a partial structure of A- and B-rings represented by formula (1) : with an alcohol represented by ROH (wherein R has the same meaning as defined above) and iodine in the absence of a rare earth compound catalyst. According to the method of the present invention, 3-alkoxy-1, 3, 5(10)-triene-6-one-steroids can be selectively produced from 19-norsteroides through a single reaction step without employment of a special catalyst.