Disclosed is a method for preparing an aromatic azoic compound by catalyzing aromatic amine with metal nanocrystals. In the method, the aromatic amine serves as a substrate, the metal nanocrystals serve as catalysts, the substrate, the catalysts and alkali are dissolved in organic solvents in normal-pressure air atmosphere, and the aromatic azoic compound is prepared by means of reaction. The method has the advantages of simplicity and convenience in process, environmental friendliness, catalyst recyclability, high universality of metal catalysts and the like, and avoids the shortcomings that environment-unfriendly metal salt catalysts or oxidants are used in an existing synthetic route, high temperature and high pressure are needed, the catalysts are poor in universality, asymmetric aromatic azoic compound is synthesized by a two-step method and the like. A series of aromatic azoic compounds can be prepared, and the method has a wide industrial application prospect.