To reduce electromagnetic pollution as well as increase the accuracy of high-precision electronic equipment, more attention has been paid to new electromagnetic wave (EMW) absorbing materials, which have the advantages of strong absorption, wide absorption bands, and a narrow thickness. In this study, a novel ternary type of the NiS₂@rGO/polypyrrole (PPy) sandwich-like structured composites was synthesized via a facile two-step method, in which the hydrothermal method was used to prepare NiS₂@rGO binary composites and then the in situ polymerization method was used to synthesize the PPy, which acted as the outer layer of the sandwich-like structure. The morphologies and electromagnetic absorption performance of the NiS₂@rGO/PPy were measured and investigated. A sample with 6 wt% NiS₂@rGO/PPy loading paraffin-composite obtained an outstanding reflection loss (RL) of −58.7 dB at 16.44 GHz under a thickness of 2.03 mm. Simultaneously, the effective electromagnetic wave absorption bandwidth for RL < −10 dB, which covered 7.04 to 18.00 GHz (10.96 GHz), was achieved by changing the thickness of the absorber from 2.0 to 3.5 mm. The results not only suggest that the NiS₂@rGO/PPy composite has excellent performance in the field of EMW absorption but also prove that the novel sandwich-like structure can contribute to appropriate impedance matching through multiple relaxation and interfacial polarization processes.