A enhanced photoluminescence red phosphor of CaTiO3:Pr,Al has been synthesized by a peroxide-based route (PBR) and high temperature sintering method. The synthesizing conditions have been optimized in this work. The effect of sintering temperature and boron on the preparation, structure, and photoluminescence were studied by X-ray powder diffraction (XRD), emission, and excitation spectra at room temperature. The red emission is attributed to 1D2 → 3H4 transition of Pr3+, and the excited energy comes from the UV absorption of host and transfers to 4f–5d band of Pr3+. Also, the studies include analysis of charge compensation and Pr3+ concentration effects. Compared with conventional solid-state reaction methods, the PBR significantly lowered temperatures of synthesis, shortened reaction time, and enhanced the photoluminescence intensity.