Electromagnetic interference (EMI) occurs when emitted signals from a device interfere with its own operation or the functioning of other electronic and wireless devices. With the increasing rate of device development and usage of electronic devices, such as laptops, mobile phones, weather radars, etc; EMI shielding has become a serious concern. In this work, we have used a unique technique to sequentially stack composite thin films to obtain a multilayered assembly. The objective of this work is to enhance the EMI shielding performance at lower shield thicknesses. Since mechanical properties are often sacrificed with increasing filler content in the composites, the rationale behind using this strategy is to retain the structural properties in the stack by interfacially stitching two immiscible polymers (PC and PVDF in this case) with a mutually miscible homopolymer (here PMMA). Besides modifying the interface, PMMA also acts as a dielectric spacer and thus contribute towards enhancing the shielding effectiveness in the stack. The average thickness of the multilayered assembly was ca. 55 µm. The SEM micrographs confirmed a diffused interface between the layers, thus proving that PMMA acted as an ‘interfacial lock’ between PVDF and PC layer. Unique ‘magnetic-semiconductor’ hybrid nanostructures (rGO-Fe3O4 and MoS2-Fe3O4) were designed using hydrothermal technique to enhance the shielding effectiveness of the stack. For effective charge transport, MWCNTs were composited with PC and in order to facilitate multiple internal reflections the hybrid structures were blended with PVDF. These two composite films were then stacked using PMMA as the interfacial modifier and the shielding effectiveness was observed to be higher in the case of rGO-Fe3O4 (-26.3 dB @ 26.5 GHz at 495 µm). The storage modulus of the stacks was observed to be much higher when compared with the individual composite films manifesting in the key role of PMMA in stitching the interface.