Expanded graphite/cobalt ferrite/polyaniline (EG/CF/PANI) ternary composites were obtained by a two-step process. The intercalation compound, CF embedded in EG, was synthesized by a coprecipitation method. PANI could then be coated on the surface of the EG/CF microparticles by in-situ polymerization to form ternary composites of EG/CF/PANI. The results indicate that the electrical and magnetic performance of EG/CF and EG/CF/PANI composites are related to their composition. The EG/CF composite with mass ratio of 1.0 has the maximal conductivity (833.33 S·cm−1) among the binary composites. Saturation magnetizations (Ms) of the EG/CF composite with mEG/mCF of 0.8 is the largest among EG/CF composites, the ternary composites of EG/CF/PANI were prepared from the EG/CF composite at this mass ratio. The electromagnetic wave absorbing property of all ternary composites excelled those of EG/CF composites, and the sample with 40 wt% of PANI has the best absorption properties in the range of 8–18 GHz frequency.