The present invention provides a method of forming a self-assembly fullerene array on the surface of a substrate, comprising the following steps: (1) providing a substrate; (2) pre-annealing the substrate at a temperature ranging from 200° C. to 1200° C. in a vacuum system; and (3) providing powdered fullerene nanoparticles and depositing them on the surface of the substrate by means of physical vapor deposition technology in the vacuum system, so as to form a self-assembly fullerene array on the surface of the substrate. The present invention also provides a fullerene embedded substrate prepared therefrom, which has excellent field emission properties and can be used as a field emitter for any field emission displays.Finally, the present invention provides a fullerene embedded substrate prepared therefrom, which can be used to substitute for semiconductor carbides as optoelectronic devices and high-temperature, high-power, or high-frequency electric devices.