In consideration of the growing electromagnetic wave (EMW) pollution and interference, it is of crucial and imperative significance to develop high-efficiency EMW absorption materials. Herein, hierarchical hybrid network of MoS@poly (3, 4-ethylenedioxythiophene) (PEDOT)/reduced graphene oxide (rGO) were successfully constructed and fabricated through the combination of oxidative polymerization and microwave-irradiated thermal reduction. The original defects in graphene oxide (GO) could be in situ repaired by introducing carbon source, and the rational regulation of polarization relaxation and conductivity of composites could be achieved. Profiting from the good impedance matching, ameliorated conductivity and enhanced dipole polarization as well as interfacial polarization by introducing GO/defect-recovered rGO and conductive PEDOT, both the MoS@PEDOT/GO and MoS@PEDOT/rGO composites exhibited outstanding EMW absorption performances. In details, the minimum reflection loss (RL) and effective absorption bandwidth (EAB) of MoS@PEDOT/GO can reach -48.65 dB at 4.5 mm, and 6.48 GHz (11.52-18 GHz) at 2.2 mm, respectively. And the EAB of MoS@PEDOT/rGO can reach 7.04 GHz (10.8-17.84 GHz) with an optimized RL of -32.41 dB at 2.1 mm under 20 wt% filler loading. Therefore, these composites can be regarded as competitive candidates for lightweight and high-efficient EMW absorbers.