Bi(2/3)‐xSmxCu3Ti4O12 (BSCTO x = 0.05, 0.10, and 0.20) ceramics are synthesized using semi‐wet technique and an extensive investigation into their structural, morphological, and elemental properties, alongside dielectric and impedance behaviors, is meticulously carried out. X‐ray powder diffraction analysis unequivocally confirmed the formation of a monophasic BCTO cubic phase without any discernible secondary phases. and the crystallite size of the BSCTO ceramic, obtained by X‐ray diffraction using Debye Scherrer formula, range from 62 to 81 nm. Rietveld analysis reveals that ceramics have a body centered cubic structure with space group Im‐3. The Scanning electron microscope image displays the dense microstructure of the ceramics, while EDX analysis unveils the elemental composition of resulting products. Doping with Sm3+ induced a notable reduction in grain size, as observed through Scanning electron microscope and Atomic Force Microscope analyses, indicating Sm3+ hindered grain growth during sintering, potentially resulting in reduced dielectric constant (ε′). Dielectric constant and dielectric loss of the composition (x = 0.2) are found to be ≈152 and 0.04, respectively at room temperature (1 kHz). Impedance characteristics revealed a substantial increase in grain boundary resistance, leading to improved dielectric loss. The AC conductivity of BSCTO ceramics exhibited a frequency‐dependent increase satisfying to Johncher's power law.