The fabrication of absorption-dominant electromagnetic interference (EMI) shielding materials is a pressing priority to prevent secondary electromagnetic pollution in miniaturized electronic devices and communication systems. Meeting this goal has remained a tough challenge to keep pace with the rapid evolution of electronics due to the complex compositional and structural design and narrow operating bands. This work articulates a sound and simple strategy to precisely modulate the electrical conductivity of reduced graphene oxide (rGO), as the building block in lightweight double-layered rGOfilm/rGO-aerogel/polyvinyl-alcohol (PVA) composites, for efficient microwave absorption over the entire Ku-band frequency range. These constructs reasonably comprised a porous absorption structure built from parallel rGO sheets aligned and prepared via freeze casting followed by freeze drying. The electrical conductivity and impedance of this layer were tuned by varying the annealing temperature from 400 to 800 °C, thereby adjusting the degree of reduction and the absorption characteristic. This layer was backed by a highly conductive rGO film reduced at a high temperature of 1000 °C, with a reflectivity of 97.5%. The incorporation of this film ensured high EMI shielding effectiveness of the double-layered structure through the absorption−reflection−reabsorption mechanism, consistent with the predicted values based on calculated loss factors and the input impedance of the structure. Accordingly, at an average EMI shielding effectiveness of 57.59 dB, the reflection shielding effectiveness (SE R ) and reflectivity (R) of the assembled composites were optimized to be as low as 0.22 dB and 0.049, respectively. This equates to approximately 99.999% shielding (SE T ) and ∼95% absorptivity (A) of the incident wave. This study opens new avenues for the development of lightweight (with a density as low as 15 mg/cm 3 ) absorption-dominant EMI shielding composite materials with promising EMI shielding efficiency and potential applications in modern electronics.