[en] Highlights: • Novel red-emitting Ba₂ZnWO₆:Eu³⁺, Li⁺ phosphors were investigated. • The effect of charge compensation agent (Li⁺) in the phosphors was analyzed. • The red emission intensity reaches a maximum with Ba₂Zn_0.8WO₆:0.1Eu³⁺, 0.1Li⁺. • The CIE chromaticity coordinates of the phosphors are all in red region. Novel red-emitting Ba₂Zn_1-x-yWO₆:xEu³⁺, yLi⁺ phosphors were prepared using a high-temperature solid-state method, and the crystal structure, the photoluminescence properties and the doping concentrations of Eu³⁺ and Li⁺ were investigated. The results show that these phosphors can be excited by near-ultraviolet light (250–400 nm) and co-doped Li⁺ can significantly enhance their PL performance. An intense red emission peak at 598 nm (⁵D₀-⁷F₁ transitions) was observed with an excitation wavelength of 316 nm. The CIE chromaticity coordinates of the phosphors are located in the red region, indicating that the BZW:Eu³⁺, Li⁺ phosphor holds promise as a red phosphor for near-ultraviolet excited WLEDs.