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Perovskite barium titanate (BaTiO3) demonstrates exceptional dielectric properties as a promising microwave-absorbing (MA) material. Leveraging structural flexibility of perovskites, magnetic components can be incorporated at A/B-sites to enhance MA performance, yet the fundamental disparity in MA mechanisms between A/B-site magnetic doping remains elusive. Herein, nickel-doped BaTiO3 perovskites were systematically synthesized through precise adjustment of the Ba/Ti molar ratio to achieve both A-site (NixBa1−xTiO3, NxBTO) and B-site (BaTi1−xNixO3, BTNxO) substitutions (0 ≤ x ≤ 0.1) via a simple one-step hydrothermal method. Notably, A-site Ni2+ substitution in NxBTO induced superior magnetic loss (tanδμ = 0.39) attributed to eddy-current dissipation, while B-site doping in BTNxO achieved higher dielectric loss (tanδε = 0.49). The N0.1BTO sample exhibited optimal MA performance with a remarkable minimum reflection loss (RLmin) of −44.39 dB and broad effective absorption bandwidth (EAB = 8.66 GHz) covering the Ku-band and 67% X-band. Multimodal analysis revealed synergistic interactions among multiple reflection and scattering, multi-polarization relaxation, natural resonance, and eddy currents. In contrast, BTN0.01O demonstrated deeper RLmin (−50.88 dB) but narrower EAB (3.33 GHz) governed by dielectric mechanisms. Structural characterization indicated A-site doping induced lattice distortion, reduced unit-cell volume, and optimized oxygen vacancy distribution, synergistically balancing magneto-dielectric parameters. Conversely, B-site substitution increased oxygen vacancy concentration and carrier mobility while amplifying dielectric fluctuations. The spatial occupation preference of A/B dopants (A-site and B-site) governs lattice symmetry breaking, consequently establishing structure–property relationships and underpinning the material’s tunable dielectric behavior and magnetic phenomena. This work proposes a site-selective doping strategy for designing high-performance perovskite MA materials through magneto-dielectric equilibrium optimization.

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