The invention provides a method for synthesizing trans-1, 1, 1, 4, 4, 4-hexafluoro-2-butene by three steps by taking 1, 1, 1-triflluoro-2, 2-dichloroethane and chloroethylene CH2=CX2 as raw materials. The method comprises the following steps: (a) in the presence of a telomerization catalyst and a catalytic addictive, carrying out reactive synthesis on 1, 1, 1-triflluoro-2, 2-dichloroethane and CH2=CX2 to obtain CF3CHClCH2CClX2; (b) carrying out photochlorination on CF3CHClCH2CClX2 to synthesize CF3CHClCH2CCl3; and (c) in the presence of a fluorination catalyst, carrying out gas phase fluorination on CF3CHClCH2CCl3 to synthesize trans-1, 1, 1, 4, 4, 4-hexafluoro-2-butene, wherein CH2=CX2 is ethylene, chloroethylene and 1, 1-dichloroethylene. The method provided by the invention has the characteristics of high trans-selectivity and low price of raw materials.