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Finding thermal history phosphors with high sensitivity and a consistent readout is required for reliable thermal history determination with high temperature resolution. This work presents a new thermal history phosphor based on the luminescence of Eu³⁺ ions in LaVO₄ to meet these requirements. As demonstrated, raising the annealing temperature causes a structural phase transition from a low-temperature tetragonal phase to a high-temperature single-stranded phase. The associated change in the local point symmetry of the crystallographic site occupied by Eu³⁺ ions result in a significant decrease in the emission intensity ratio of the ⁵D₀ → ⁷F₂ band relative to the ⁵D₀ → ⁷F₁ band, which enables the development of the ratiometric thermal history phosphor with the relative sensitivity of 0.38% °C⁻¹ at 800 °C. Its applicative potential for thermal history readout was proved in the proof-of-concept experiment. © 2023 The Royal Society of Chemistry.