Herein, we report the gadolinium-doped MoS2-reduced graphene oxide (Gd@MoS2-rGO) nanocomposite by using a facile two-step hydrothermal method for high-performance electromagnetic interference (EMI) shielding applications. Structural and microstructural properties of MoS2-rGO and Gd@MoS2-rGO nanocomposite were investigated by scanning electron microscope, transmission electron microscope, X-ray diffraction, and Raman spectroscopy. Gd-doping content in MoS2-rGO nanocomposite has successively increased the electrical conductivity to improve imaginary permittivity (ε″) and dielectric loss tangent (tanδε) in the frequency range of 8.0–12.0 GHz. Pure MoS2-rGO nanocomposite exhibits low total shielding effectiveness (SET ∼ 16.18 dB) in entire frequency range as compared to 10% Gd@ MoS2-rGO (SET ∼ 19.25 dB) and 20% Gd@ MoS2-rGO (SET ∼ 20.47 dB) nanocomposite. In this work, Gd act as a highly conductive network between MoS2 and rGO nanosheet coupled with a large surface area, which leads to the migration of fast charge carriers at multi-interfaces. The results suggest that the Gd@MoS2-rGO nanocomposite have great potential applications as a candidate for a new type of microwave absorption and EMI shielding material. •First-time report Gd@MoS2-rGO nanocomposite by two-step hydrothermal method.•Higher conductivity and dielectric loss for 20% Gd@MoS2-rGO nanocomposite.•Most of the EM energy attenuated by 20% Gd@MoS2-rGO nanocomposite.