Eu3+-doped CaTiO3 perovskites were prepared using a sol-gel reaction method. Two solvent materials were employed to the synthesis process to produce higher emitting phosphors. Eu3+-doped CaTiO3 perovskite synthesized using an ethanol mixture solvent exhibited higher photoluminescence intensities for red emission than those synthesized using distilled water as a solvent. Ni ion-loaded CaTiO3:Eu3+ perovskite showed enhanced red emission and higher photocatalytic activities compared to those of bare CaTiO3:Eu3+ perovskite. The improvement of the photocatalytic degradation of toluene was attributed to the lower bandgap of Ni ion-loaded CaTiO3:Eu3+ perovskite, as determined by UV-visible diffuse reflectance spectroscopy.