The invention discloses a process for synthesizing sex pheromone of pine caterpillar, which employs 2-hexyne-1-alcohol as an initial raw material, three-bond positional transference is carried out under the effect of lithium and propane diamine to obtain 5-hexyne-1-alcohol; under acidic condition, 5-hexyne-1-alcohol is reacted with dihydropyran to obtain 1-THP-5-hexyne-1-alcohol protected by THP on hydroxyl, Under co-catalysis of metal palladium and cuprous iodide, 1-THP-5-hexyne-1-alcohol and trans-dichloroethylene are subjected to coupling reaction to generate conjugate enyne(7E)-1-THP-8-chlorine-5-alkyne-7-alkene-1-octanol; under the catalysis of metallic iron, (7E)-1-THP-8-chlorine-5-alkyne-7-alkene-1-octanol and a n-Butyl bromide grignard reagent are further subjected to coupling reaction to obtain (7E)-1-THP-5-alkyne-7-alkene-1-dodecanol, under the catalytic reduction of metal zinc, (5Z, 7E)-1-THP-dodecanol dienol; under the camphor sulfonic acid condition, (5Z, 7E)-1-THP-dodecanol dienol removes the THP protective group to obtain the final target product (5Z, 7E)-dodecanol dienol. The method of the invention has the advantages of easily available synthesis raw materials, low cost, mild reaction condition, easy operation, high yield and good stereoselectivity.