The invention provides a preparation method of core-shell carbon nano-tube hybridization packing with an epoxy group. The preparation method is mainly characterized in that two monomers are absorbed onto the surface of a carbon tube by using an effect of a multi-wall carbon nano-tube on absorbing small molecules, and azodiisobutyronitrile (AIBN) is used for activating the surface of the carbon nano-tube to generate an active free radical center and to trigger the copolymerization of divinyl benzene and glycidyl methacrylate, so that the purposes of covering the carbon tube and introducing functional groups are realized. The preparation process comprises: firstly ultrasonically dispersing the multi-wall carbon nano-tube in a solvent, then adding two monomers, stirring, introducing nitrogen, and heating to facilitate the reaction. A composite material with adjustable electrical performance is prepared in the method; moreover, the epoxy group and ester group are introduced onto the surface of the carbon tube, so that the reactivity and compatibility between the carbon tube and matrixes such as epoxy resin, polyester and polyamide can be improved, and a great significance on improving the performance of the composite material can be realized. The preparation method has the advantages of simple process, flexible and wide applicability, wide industrialization prospect and the like.