Observation of at least two coexisting switchable ferroic states viz., ferromagnetic, ferroelectric, and/or ferroelastic at room temperature with promising coupling among order parameters, has made BiFeO3 a highly explored material in the field of multiferroics and/or magnetoelectric multiferroics, which creates the possibility for its application in various technological devices such as spintronics, spin-valve, DRAM, actuators, sensors, solar-cells photovoltaic, etc. Intrinsically, its low coupling coefficients, difficulty to prepare in pure phase in bulk, high leakage current, etc. have restricted BiFeO3 from technological reliability. However, the effect of doping with iso- and alio-valent ions, nanostructure, thin-film-form and nanoparticles, etc., has been carried out to improve its physical properties by several research groups over the decades. In this chapter, the structural, luminescence, and dielectric properties of samarium (Sm3+) doped BiFeO3 nanoceramics synthesized using a modified gelcombustion route are discussed in detail. The effect of Sm3+ doping in BiFeO3 is explored using the X-ray diffraction (XRD) technique. The XRD studies exhibit a possible structural phase transition above Sm3+ doping of 15% from rhombohedral (R3c) space group to the orthorhombic (Pbnm) space group. The dielectric study shows interesting behavior accompanied by structural transition. Our study suggests that Sm3+ doping plays an important role in governing the structural, luminescence, and dielectric properties of BiFeO3 samples.