Ceramics of the quasi-binary concentration section (0.1 ≤ x ≤ 0.2, Δx = 0.025) of the ternary solid solution system (0.5 − x)BiFeO3-0.5PbFe0.5Nb0.5O3-xPbTiO3 were prepared by the conventional solid-phase reaction method. An X-ray study at different temperatures revealed that (0.5 − x)BF-0.5PFN-xPT ceramics have a cluster morphology. Clusters have different modulation, crystal lattice symmetry, and chemical composition. The presence of a cluster structure in a solid solution with heterovalent substitution, consisting of regions rich in Ti+4, Nb+5, or Fe3+, has led to the appearance of Maxwell–Wagner polarization in the studied ceramics. The study of the dielectric characteristics revealed the relaxor-like behavior of the studied ceramics. The grain morphology, dielectric, pyroelectric, and piezoelectric properties of the selected solid solutions were investigated. The highest piezoelectric coefficient, d33 = 280 pC/N, was obtained in the 0.3BiFeO3-0.5PbFe0.5Nb0.5O3-0.2PbTiO3 ceramics. Study of the dielectric characteristics of all samples revealed relaxor ferroelectric behavior and a region of diffuse phase transition from the paraelectric to ferroelectric phase in the temperature range of 140–170 °C.