The invention relates to a preparation method of a fulvestrant related substance E. The invention relates to a preparation method of a fulvestrant related substance E shown as a formula I (See the specification for reference), namely, 7-[9-(4, 4, 5, 5, 5-pentafluoropentylsulfinyl) nonyl] estra-1, 3, 5(10), 6-tetraene-3, 17 beta-diol. The fulvestrant related substance E is obtained by taking (7S, 8R, 9S, 13S, 14S, 17S)-3, 17-dihydroxy-13-methyl-7-(9-((4, 4, 5, 5, 5-pentafluoropentyl) sulfo) nonyl)-7, 8, 9, 11, 12, 13, 14, 15, 16, 17-decahydro-6H-cyclopentadiene-6-ketone as a starting material through the reaction steps of protection, reduction, oxidation, dehydration and deprotection. The method has the advantages of few side reactions, high product yield, good purity, reasonable process design, simple operation and low cost.