The conducting polymer-coated multi-walled carbon nanotubes (MWCNTs) were prepared by template polymerization of aniline and pyrrole on the surface of MWCNTs in order to develop the novel electromagnetic interference (EMI) shielding materials. The conducting polymer phases formed on the surface of MWCNTs were confirmed by field emission-scanning electron microscopy and field emission-transmission electron microscopy. Both permittivity and permeability were significantly improved for the conducting polymer-coated MWCNTs due to the intrinsic electrical properties of MWCNTs and the conducting properties of coated polymers. The electromagnetic waves were effectively absorbed based on the permittivity nature of conducting polymer and MWCNTs preventing the secondary interference from reflecting the electromagnetic waves. The highly improved EMI shielding efficiency was also obtained for the conducting polymer-coated MWCNTs showing the synergistic effects by combining MWCNTs and the conducting polymers.