Pr3+-related intervalence charge transfer (IVCT) bands are a research hotspot owing to their amelioration in the luminescence thermal quenching of Pr3+-activated phosphors. Here, a typical IVCT band displacement strategy via a topological chemical scheme is reported to optimize the luminescence thermal quenching performance of praseodymium-doped niobo-tantalate. The substitution of Ta5+ ions for Nb5+ ions reduces the valence-weighted average cation optical electronegativity and increases the bond lengths of the activator (Pr3+) to the ligand cations (Nb5+ and Ta5+) via adjusting the crystal structure, leading to an increase in the IVCT energy level position from 3.521 to 4.139 eV. The increase in the IVCT energy level leads to an increase in the number of electrons located in the Pr3+ 3P0 energy level, which compensates for the emission of 1D2 during warming. Especially, the energy gap value of the IVCT band is positively correlated with the thermal quenching activation energy ΔE2. ΔE2 increases, the crossover point rises, and the nonradiative transition decreases, further enhancing the Pr3+ 1D2 emission. At 503 K, the 1D2 emission integral intensity increases from 14 to 224% relative to the 303 K original integral intensity. This IVCT band displacement strategy can be used as a scheme for designing antithermal quenching luminescence materials.