Enhancement of the 1D2–3H4 red emission in CaTiO3:Pr3+ with addition of nanosized SiO2 fabricated by a solid state reaction method is reported. The dynamical processes for the improvement of red emission were systematically investigated using photoluminescence (PL) and PL excitation spectra, and diffused reflectance spectra as well as time decay patterns of PL and persistent afterglow. Higher efficiency of energy transfer from CaTiO3 host to the activator Pr3+ due to the improvement of crystallinity by SiO2 addition was discussed in comparison with that of the SiO2 free sample. The enhancement of persistent afterglow after the cessation of excitation in SiO2 added CaTiO3:Pr3+ was also analyzed by theoretically fitted results.