Europium (Eu3+)-doped CaZnTiO3 perovskite phosphors were synthesized using a sol-gel reaction method. Different solvent materials were introduced to the synthesis process to produce higher emitting phosphors. Eu3+-doped CaZnTiO3 perovskite synthesized using an ethanol mixture solvent exhibited higher photoluminescence intensities for red emission than those synthesized using distilled water as a solvent. The synthesized Eu3+-doped CaZnTiO3 perovskites were characterized by photo-physical analysis and tested for the photocatalytic degradation of toluene. Ru, Co, and Ni ions were loaded on the perovskites to improve photocatalytic activity. Ni ion-loaded CaZnTiO3 : Eu3+ perovskite showed enhanced red emission and higher photocatalytic activities compared to those of bare CaZnTiO3 : Eu3+ perovskite. The improvement of the photocatalytic degradation of toluene was attributed to the lower bandgap of Ni ion-loaded CaZnTiO3 : Eu3+ perovskite, as determined by UV-visible diffuse reflectance spectroscopy.