The invention discloses a method of catalytic preparation of 4-aminodiphenylamine by a Ni-B amorphous alloy-loaded catalyst, comprising the following steps: (1) mixing the aniline and the water solution of alkali, distilling to obtain aniline-water azeotrope; (2) adding the nitrobenzene to react; (3) adding the water and the Ni-B amorphous alloy loaded catalyst, and introducing the hydrogen; and (4) performing the solid-liquid separation to obtain the Ni-B amorphous alloy loaded catalyst and the liquid phase, and feeding the Ni-B amorphous alloy loaded catalyst back to the step (3); and performing the phase separation on the liquid phase to obtain the organic phase and the water solution of the alkali, rectifying the organic phase to obtain the product of 4-aminodiphenylamine, and simultaneously recovering the aniline and feeding the water solution of the alkali back to the step (1). In the method provided by the invention, the catalyst with the price lower than that of the noble metal catalyst is used, and simultaneously the direct hydrogenation on the azobenzene/azoxybenzene and/or the hydroazobenzene is carried out to form the aniline in the step of hydrogenation reaction, thereby shortening the process of the production technology and reducing the production cost.