The invention relates to a preparation method of 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl. The preparation method comprises the following steps: synthesizing 3,3'-bis(trifluoromethyl)hydrazo-benzene in an inorganic alkaline aqueous solution by adopting nitrobenzotrifluoride as a raw material, adopting a phase transfer catalyst, a co-catalyst and Pd/C as a catalytic system and adopting aromatic hydrocarbon as a solvent, and performing the re-arrangement reaction on the 3,3'-bis(trifluoromethyl)hydrazo-benzene in an inorganic acid aqueous solution, thus obtaining 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl, wherein the phase transfer catalyst is one or a mixture of more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and cetyl trimethyl ammonium bromide, and the co-catalyst is one or a mixture of more of 2,3-dichloro-1,4-naphthoquinone, 2-hydroxyanthraquinone and 2,6-dioxyanthraquinone. The preparation method has the advantages of mild reaction condition, simple process, high product quality and yield, low production cost, environmental friendliness, suitability for continuous production and the like.