This invention relates to synthetic method of a ( E, E) - geranyl linalool. The invention takes (E) - nerolidol as raw material. The hydroxyl is shield by dihydropyrane, gain ( E) - nerolidol tetrahydropyrane aether; selenium dioxide and teri-butyl hydroperoxide selectively oxidize the anti-form methyl of ( E) - nerolidol tetrahydropyrane aether to gain anti-form allyl position hydroxylated oxidative product ( E, E) - 12 - hydroxy nerolidol tetrahydropyrane aether, transit halogenating reaction to gain ( E, E) - 12 - halogeno- nerolidol tetrahydropyrane aether, then take reaction with isopropyl methyl ketone that is selectively divested one proton by diisopropyl amido lithium, generate ( 6E, 10E) - 2, 6, 10, 14 - tetramethyl - 14 - ( tetrahydropyrane - 2 - oxygen) -16 - 6, 10, 15 - triene - 3 - ketone, use sodium borohydride to reduce to gain ( 6E, 10E) - 2, 6, 10, 14 - tetramethyl - 14 - ( tetrahydropyrane - 2 - oxygen) -16 - 6, 10, 15 - triene - 3 - alcohol, takes reaction with sulfonyl chloride or sulphonic acid ester with alkali presence to gain ( 6E, 10E) - 2, 6, 10, 14 - tetramethyl - 14 - ( tetrahydropyrane - 2 oxygen) -16 - 6, 10, 15 - triene - 3 - alcoholic sulphonic acid ester, then divide sulphonic acid ester group under base catalysis to gain ( E, E) - geranyl linalool tetrahydropyrane aether, and by deprotection to gain ( E, E) - geranyl linalool. ËFor the configuration of ( E) - nerolidol 3 position tertiary carbon is not influenced in the course of reaction, if use ( E) - nerolidol that has optical activity as raw material, should gain optical active ( E, E) - geranyl linalool. ((E, E)-geranyl linalool can replace Teprenone and such type medicament intermediate, natural product intermediate, insect pheromone and spice etc.