Composite materials based on NiFeO nanoparticles and polyethylene matrix have been synthesized by thermal decomposition to expand the application area of high-pressure polyethylene by filling it with nanoscale particles. The synthesized compositions were obtained in the form of a dark gray powder and compressed for further study According to TEM, the average particle size in composites was 2, 3, and 4 nm in samples with a filling of 10%, 20% and 30%. The concentration dependences of the specific electrical resistivity ρ, dielectric permittivity ε, saturation magnetization M and the parameters of reflection and attenuation of microwave power of the obtained composites were investigated. The threshold for percolation in such materials is found to be within a concentration range of 20…30%. The electronic and atomic structure of composites was studied by methods of Mössbauer spectroscopy, X-ray diffraction and X-ray absorption spectroscopy. The closest atomic environment of nickel and iron in nanoparticles is close to that of crystalline NiFeO. The dependence of the nanoparticles size as well as the dependence of the number of tetrahedral or octahedral iron positions in nickel ferrite nanoparticles to their content in polyethylene matrix is established. It is shown that composite materials based on NiFeO nanoparticles and polyethylene matrix can be used as components of electromagnetic compatibility systems.