Pr-doped barium titanate-calcium titanate with rich barium is prepared by a sol-gel technique. A relatively strong red luminescence is observed in the material when Pr-BaTiO3 material does not exhibit obvious red luminescence. The wavelength range of luminescence near red light is broad. The phenomenon is discussed with respect to the substitute of Ca and the two-photon luminescence effect. The experimental results provide a possible way to develop new materials with photoluminescence properties that can be controlled by external fields because the microscopic structure of BaTiO3 can be changed by temperature, stress, electric field, and so on. [ABSTRACT FROM AUTHOR]