Polycrystalline samples BaTiO3 and the solid solutions Ba0.9Sr0.1TiO3, Ba0.9Sr0.1Ti0.9Sn0.1O3, Ba0.9Sr0.1Ti0.8Sn0.2O3 were obtained by means of a mechanochemical treatment based on the high-energy ball milling technique and next a high temperature solid state reaction method. The influence of synthesis condition on microstructural, dielectric and ferroelectric properties of obtained solid solutions were investigated. The structure and morphology of the investigated samples were characterized by an X-ray diffraction (XRD) and scanning electron microscopy (SEM). The characterization of electrical properties of the ceramics within the temperature range from –130°C to 250°C were performed by means of a dielectric spectroscopy method at the frequency ranging from 0.1 Hz to 10 MHz. The diffusion of the paraelectric – ferroelectric phase transition and dielectric relaxation for ceramic samples are described.