<p>This work presents Mn⁴⁺-activated LaAlO₃ synthesized by the solution combustion method using urea as a fuel for the combustion process. Fuel amount (<i>n</i>) and annealing temperature are two important factors of the solution combustion process, which decide the quality of the obtained LaAlO₃:Mn⁴⁺ phosphors. Analysis of X-ray diffraction, SEM images, photoluminescence (PL), and photoluminescence excitation (PLE) spectra of the prepared LaAlO₃:Mn⁴⁺ samples indicated that the optimal values of fuel amount and annealing temperature are n=14 and 600°C, respectively. The LaAlO₃:Mn⁴⁺ materials were also fabricated with various Mn⁴⁺ concentrations and the optimal concentrations for the Mn⁴⁺ emission was found to be at 2.0 mol%, which shows the strongest emission peaking at 700 and 725 nm that are due to the internal splitting of the ²E_g <InlineEquation ID="IEq1"> <EquationSource Format="TEX">\(\rightarrow\)</EquationSource> <EquationSource Format="MATHML"><math> <mo stretchy="false">→</mo> </math></EquationSource> </InlineEquation> ⁴A_2g transition of Mn⁴⁺ ions. CIE coordinates of the prepared samples showed that the LAM-2 sample not only reaches the strongest emission intensity but also emits the deep-red color (0.7165-0.2833) that is suitable for applications in white-light devices, and agricultural light. The Racah parameters <i>B</i>, <i>C</i>, and the crystal field splitting parameter <i>Dq</i> of the Tanabe–Sugano (T–S) diagram were also determined from the PL and PLE spectra of the LaAlO₃:Mn⁴⁺ phosphors, and the results indicated that the Mn⁴⁺ emission occurs in the strong crystal field.</p>