Solid solutions of Pb1-xSmx[Zr0.50Ti0.45(Mo1/3In2/3)0.05]1-x/4O3, known as PSZT-PMI, were successfully synthesized using the mixed oxide method at high temperature. The concentrations of Sm+3 varied (x = 0.03, 0.08, 0.10, and 0.12). The resulting ceramic samples underwent sintering at 1250°C, followed by comprehensive analysis utilizing various laboratory techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), density measurement, dielectric measurements, and Raman spectroscopy. The XRD analysis confirmed the crystallization of the ceramics in a tetragonal phase structure. Among the samples, the one with 8% Sm3+ exhibited the highest experimental density, measuring 92.6641%. Remarkably, this particular ceramic sample also demonstrated exceptional dielectric properties, characterized by a relative permittivity (εr) of 12503.59, a loss tangent (tanδ) of 0.04168, and a Curie temperature (Tc) of 635K. SEM micrographs revealed the presence of uniformly distributed grains with varying shapes and sizes across the entire surface of the samples.