The invention provides a ceramic coating of an exhaust pipe and a preparation method thereof. The ceramic coating comprises a bonding bottom layer, a second transition layer, a third transition layer,a fourth transition layer and a surface layer which are sequentially coated on the inner surface of an exhaust pipe from bottom to top; the preparation method comprises the following steps that the inner surface of the exhaust pipe is pretreated; the powder is preset by adopting an electrostatic spraying method to obtain a preset layer; and electron beam welding is carried out on the preset layerto obtain the ceramic coating. According to the coating and the method, the ceramic coating has the outstanding performance of high hardness, high strength, oxidation resistance, wear resistance, high temperature resistance, thermal shock resistance and the like, the bonding strength between the ceramic layer and a metal substrate is effectively improved, and the high-temperature oxidation resistance of the surface layer is improved.