A novel synthetic route of Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz)was developed. It contains three-step reactions as follows: (1) The vapor-phase catalytic fluorination from hexachlorobutadiene to (E/Z)-2,3-dichlorohexafluoro-2-butenepromoted by Cr-based catalyst; (2) The liquid-phase dechlorination reaction from (E/Z)-2,3-dichlorohexafluoro-2-butene to 1,1,1,4,4,4-hexafluoro-2-butyne with Zn in DMF; (3) The gas-phase hydrogenation reaction from 1,1,1,4,4,4-hexafluoro-2-butyne to Z-HFO-1336mzz promoted by Pd+Bi/PAF (porous aluminium fluoride) catalyst. It provided a potential method for industrial production of Z-HFO-1336mzz.