The invention relates to an electric conduction composite material with a poly-2, 3-dimethylaniline/polyaniline core shell structure, and a preparation method of the electric conduction composite material. In the composite material, the poly-2, 3-dimethylaniline is used as a core, and the polyaniline is used as a shell. The preparation method comprises the following steps: the poly-2,3-dimethylaniline is firstly prepared by a solution polymerization process, and then is filtered, washed, dried and ground to obtain the powdered poly-2,3-dimethylaniline; and the powered poly-2, 3-dimethylaniline is used as the core, polymerization is carried out to the surface of the powered poly-2, 3-dimethylaniline by the solution polymerization process or emulsion polymerization process, and then a product is filtered, washed, dried and ground to obtain the electric conduction composite material with the poly-2, 3-dimethylaniline/polyaniline core shell structure. In the electric conduction composite material with the poly-2, 3-dimethylaniline/polyaniline core shell structure, the electric conductivity of the poly-2, 3-dimethylaniline/polyaniline is remarkably improved, thereby being beneficial tobeing applied to the field of sensors, electric conductive devices, electrode active materials and the like.