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Non-stoichiometric lead free polycrystalline Sr0.8Sn0.2Bi1.75Sm0.25Nb2O9 (SSBSN) ferroelectric ceramics were synthesized through conventional solid step route method by incorporating ball milling and microwave sintering method. X-ray diffraction along with the Rietveld refinement technique confirms the single-phase orthorhombic structure with A21 crystal symmetry. Additionally, the short-range ordering was confirmed by Raman spectroscopy. Doping induced crystallite size and strain were further calculated from the Williamson-Hall plot, which comes around 150 nm and 1.48 × 10–3 respectively. A plate like morphology with an average grain size of 0.41 μm was confirmed by scanning electron microscopy (SEM). A diffuse type ferroelectric to paraelectric phase transition was recorded at 395 °C, mostly arising due to structural heterogeneity at the inter-ferroelectric phase boundary. The temperature and frequency-dependent dielectric measurement of SSBSN ceramic reveal a Maxwell–Wagner relaxation, with prominent dielectric loss in a low frequency regime perhaps due to the generation of leakage current in the SSBSN system. Frequency dependent ac conductivity indicates the polaron assisted hopping mechanism in SSBSN, which further obeys Jonscher’s formulation. The intra and intergranular contributions to impedance in SSBSN ceramics were probed by the complex impedance spectroscopy (CIS) technique. A non-Debye type relaxation mechanism in SSBSN ceramics was indicated by the Cole–Cole plot, whereas the conduction mechanism and transport properties were briefly studied using modulus spectroscopy. [ABSTRACT FROM AUTHOR]