Electromagnetic pollution presents growing challenges due to the rapid expansion of portable electronic and communication systems, necessitating lightweight materials with superior shielding capabilities. While prior studies focused on enhancing electromagnetic interference (EMI) shielding effectiveness (SE), less attention is given to absorption‐dominant shielding mechanisms, which mitigate secondary pollution. By leveraging material science and engineering design, a layered structure is developed comprising rGOnR/MXene‐PDMS nanocomposite and a MXene film, demonstrating exceptional EMI shielding and ultra‐high electromagnetic wave absorption. The 3D interconnected network of the nanocomposite, with lower conductivity (10−3–10−2 S/cm), facilitates a tuned impedance matching layer with effective dielectric permittivity, and high attenuation capability through conduction loss, polarization loss at heterogeneous interfaces, and multiple scattering and reflections. Additionally, the higher conductivity MXene layer exhibits superior SE, reflecting passed electromagnetic waves back to the nanocomposite for further attenuation due to a π/2 phase shift between incident and back‐surface reflected electromagnetic waves. The synergistic effect of the layered structures markedly enhances total SE to 54.1 dB over the Ku‐band at a 2.5 mm thickness. Furthermore, the study investigates the impact of hybridized layered structure on reducing the minimum required thickness to achieve a peak absorption (A) power of 0.88 at a 2.5 mm thickness.