A novel ultra-thin three-layered assembly of different nano-structured polymer blends is designed here for attenuating electromagnetic (EM) waves by 99.999%. All the key parameters1; intrinsic wave impedance matching, intense absorption of the incoming EM radiation and surface reflection of incident EM waves from the shield material were targeted to design the final assembly using inclusion of chemically modified nano materials in an immiscible bi-component blends of PC (poly carbonate) and PVDF (polyvinylidene fluoride). Acid functionalized MWCNTs contained blend was used as a front layer of the assembly which guided the maximum incident EM wave into the assembly due to the intrinsic impedance matching. In the middle layer α-MnO2 doped MWCNTs and ferrite-doped cross-linked GO framework contained blend facilitated the enhanced attenuation of incident EM wave by absorption due to the high dielectric and magnetic loss parameters. Surface reflection phenomenon was utilized here at the final layer of the assembly, which directed the penetrated waves to the middle layer of the assembly for secondary interaction, when only MWCNTs were present in the blend. Surely, this unique study offers amendable replacement of the existing solution related to EM absorption.