Core-shell structures and interfacial polarization are of great significance to meet the diversified requirements of microwave attenuation. Herein, α-Fe2O3@MoS2 nanocomposites are fabricated via a simple two-step hydrothermal process, in which MoS2 nanosheets as shell are self-assembled and α-Fe2O3 microdrums as core to constitute special flower-like morphology with core-shell structure. This structure can provide more interfaces contact to achieve strong interfacial polarization and possibly offer more multiple reflection and scattering of electromagnetic wave. Furthermore, the microwave dissipation performances of α-Fe2O3@MoS2 nanocomposites can be significantly improved through constructing of core-shell structure and flower-like morphology, controlling the content of α-Fe2O3 microdrums and adjusting the filler loading ratios. This work proves that the as-synthesized nanocomposites achieve excellent effective absorption bandwidth and outstanding electromagnetic wave absorption capabilities due to its special interfaces, core-shell structures and good impedance matching conditions. Therefore, α-Fe2O3@MoS2 nanocomposites are expected to be a novel and desirable candidate for high-performance electromagnetic wave absorbers.