Red long afterglow CaTiO3: Pr, Al phosphors have been synthesized by sol-gel method using ethanol as solvent and citric acid as a chelating agent. TG-DTG curves and X-ray diffraction analysis indicate that crystalline calcium titanate has been synthesized at calcining temperature of 700 °C for 5 h. Photoluminescence and decay curves indicate that the luminescence properties of phosphors synthesized by sol-gel method are better than that prepared by solid-state reaction and the sample heated at 900 °C exhibits the optimal luminous property. Using ultrasonic dispersing technique improved the luminescence properties of phosphors.