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Pure-phase LiAl₅O₈:Cr³⁺ leaf-like particles were synthesized by combustion synthetic route at various concentrations. Both sharp peaks and broad emission photoluminescence are apparent even at room temperature. The most optimum doping concentration of 0.75 % based on lifetime and emission intensity was chosen. Peaks of different configurations were separated by deconvolution from 120 K to 680 K, where ⁴T₂ peak increases in temperature to the expense of the sharp ²E emissions, giving luminescence intensity ratio (LIR) relative sensitivity of 2.8 % K⁻¹ at room temperature. Large separation between Cr³⁺ R lines marks their LIR as perspective at low temperatures. At high temperatures luminescence lifetime provided for 0.8 % K⁻¹ sensitivity, while line-shift and bandwidth methods are not sensitive enough for thermometric applications. Deconvolution of peaks enabled for 10 % more precise estimation of Debye temperature (679 K). © 2024 Korean Physical Society