Ceramic samples with perovskite structure of Ba0.9Ca0.1Zr0.05M0.10Ti0.85O3 (M = Mn, Fe, Co) were obtained by standard solid-phase synthesis methods. The processes of phase formation of samples by methods of X-ray phase analysis have been investigated, the parameters of unit cells have been determined. Magnetic and optical properties of the obtained samples were investigated by methods of magnetic susceptibility and diffuse reflection spectroscopy. It was found that the phase composition, as well as magnetic and optical properties depend on the nature of the introduced paramagnetic element.