The invention provides a preparation method of 1,1,1,2,3-pentachloropropane, the method uses 1,1,1,3-tetrachloropropane as raw material, 1,1,1,2,3- Pentachloropropane is used as a solvent, and dehydrochlorination reaction is carried out to obtain 1,1,3-trichloropropene, chlorine gas is introduced into the reaction system after the reaction, and chlorination reaction is carried out to obtain 1,1,1,2,3-pentachloropropane , in the present invention, 1,1,1,2,3-pentachloropropane is used as a solvent or diluent, and can be used as a solvent to prevent high boilers such as dimers, oligomers or polymers from being produced in the process of dehydrochlorination The inhibitor can increase the conversion rate of 1,1,1,3-tetrachloropropane and the yield of the final product 1,1,1,2,3-pentachloropropane. The preparation method of the invention can be used in the production mode of batch reaction, and can also be used in the production mode of continuous reaction, is suitable for industrial production, and has wide application prospects.