The network structure of Ni-coated carbon black (NCB) composites filled with phenolic resin was investigated by means of using scanning electron microscopy, viscosity, interfacial tension, shrinkability, Flory-Huggins interaction parameters, and swelling index. The electrical properties of the composites have been characterized by measurement of the specific conductivity as a function of temperature. Additionally, the variation of conductivity with temperature for the composites has been reported and analyzed in terms of the dilution volume fraction, relative volume expansion, and barrier heights energy. The thermal stability of phenolic-NCB composites has been also studied by means of the voltage cycle processes. The experimental data of EMI wave shielding were analyzed and compared with theoretical calculations. The mechanical properties such as tensile strength, tensile modulus, hardness and elongation at break (EB) of NCB-phenolic resin composites were also investigated.