In highly sophisticated electronic devices, research on electromagnetic interference (EMI) shielding materials is a crucial aspect. This study introduces a ternary thermoplastic fluoropolymer blend nanocomposite (NC) system for improved EMI shielding, consisting of polyvinyl dimethylamine fluoride (PVDF) and Fe3O4‐MWCNT (1:2) NC. Employing a hydrothermal process, complex hierarchical nanostructures (NS) of Fe3O4‐MWCNT (1:2) NC are produced. These NS are then integrated using a drop‐casting technique into PVDF matrices with different weight % (20 wt.%, 40 wt.%, and 60 wt.%) and thicknesses (20 μm, 50 μm, and 80 μm). The single‐layer thin films (SLFs) with the Fe3O4‐MWCNT (1:2)‐PVDF matrix are successfully produced as a consequence of this approach. Fe–O–C bonding from XPS analysis confirms chemical interaction, while SEM–EDX imaging analysis for composition materials wt.% and material homogeneity. Moreover, the SLFs of Fe3O4‐MWCNT (1:2)‐PVDF (20 wt.%, 40 wt.%, and 60 wt.% for 80 μm thickness) are newly discovered meta‐nanocomposites (MNCs) properties, which is evidenced by negative microwave (MW) real complex permittivity (‐274.4, ‐271.2 and ‐136.4), superior attenuation constant (12862.73, 16265.18 and 12256.34) and higher AC electrical conductivities (1020.8, 1174.6 and 727.7 S.m−1. The synergistic impact of higher attenuation and AC conductivity of MNCs results in an increased average MW shielding effectiveness (SE) of ∽ 33.28 dB for Fe3O4‐MWCNT (1:2)‐PVDF 20 wt.% MNCs (∽ 80 μm).This article is protected by copyright. All rights reserved.