The co-doping effect of aliovalent metal ions such as Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, and Zn²⁺ on the photoluminescence of the Y₂O₃:Eu³⁺ red phosphor, prepared by spray pyrolysis, is analyzed. Mg²⁺ metal doping is found to be helpful for enhancing the luminescence of Y₂O₃:Eu³⁺. When comparing the luminescence intensity at the optimum doping level of each Mg²⁺ ion, the emission enhancement shows the order of Zn²⁺ ≈ Ba²⁺ > Ca²⁺ > Sr³⁺> Mg²⁺. The highest emission occurs when doping approximately 1.3% Zn²⁺, which is approximately 127% of the luminescence intensity of pure Y₂O₃:Eu³⁺. The highest emission was about 127% of the luminescence intensity of pure Y₂O₃:Eu³⁺ when doping about 1.3% Zn²⁺. It is determined that the reason (Y, M)2O3:Eu³⁺ has improved luminescence compared to that of Y₂O₃:Eu³⁺ is because the crystallinity of the matrix is improved and the non-luminous defects are reduced, even though local lattice strain is formed by the doping of aliovalent metal. Further improvement of the luminescence is achieved while reducing the particle size by using Li₂CO₃ as a flux with organic additives.