Inorganic perovskite-oriented materials are renowned for their multifunctional characteristics, making them candidates for various advanced applications. This study focuses on the synthesis and characterization of a novel inorganic perovskite material, (Ni0.5Sm0.5FeO3)0.5(BaTiO3)0.5, prepared via the cost-effective solid-state reaction method. Detailed structural and microstructural analyses were conducted to determine phase formation and grain size effects. Rietveld analysis was employed to identify the crystallographic phases, while field emission scanning electron microscopy (FE-SEM) provided insights into the sample’s morphology. FTIR and RAMAN spectroscopy were used to investigate the vibrational modes of the material. The dielectric properties and electrical characteristics were measured across a range of frequencies and temperatures using an impedance analyzer. The material’s potential for energy storage and NTC-type thermistor applications was evaluated through its temperature coefficient of resistance (TCR) and thermistor constant (β) analysis. Additionally, the ferromagnetic property was assessed through M−H hysteresis loop analysis, highlighting the material’s multifunctional capabilities.