<p>Cr³⁺/Bi³⁺ co-doped and Cr³⁺/Yb³⁺ co-doped La₂LiSbO₆ phosphors have been synthesized via a high-temperature solid-state method, respectively. La₂LiSbO₆: Cr³⁺ gives a broadband emission peaking at 855&#xa0;nm under 671&#xa0;nm excitation. Partial substitution of La³⁺ ions by Bi³⁺ ions induces lattice distortion in the La₂LiSbO₆ host and weakens the crystal field strength of Cr³⁺, leading to the red shift of Cr³⁺ emission. The Cr³⁺ emission peak shifts from 855 to 900&#xa0;nm with Bi³⁺ concentration increasing from 0 to 0.07&#xa0;mol %. The increased lattice distortion also improves the local environment of Cr³⁺, thereby resulting in a threefold increase in luminescence intensity and a 25.8% increase in quantum yield. When the Yb³⁺ ions are introduced, the emission peak can be further tuned from 855 to 1000&#xa0;nm directly, induced by energy transfer from Cr³⁺ to Yb³⁺ ions. It is proven that quadrupole–quadrupole interaction is responsible for the energy transfer from Cr³⁺ to Yb³⁺ in the La₂LiSbO₆ host. Moreover, the introduced Yb³⁺ also largely improves the thermal stability of the phosphor. The work might provide meaningful reference for the design and development of highly efficient Cr³⁺-doped luminescent materials.</p>