Two series of phosphors, α-Sr_2(1−x)Dy_2xP₂O₇ and α-Sr_2(1−2x)Dy_2xLi_2xP₂O₇, with different x values were synthesized successfully using a conventional solid-state method at high temperature for the first time, and their luminescence properties were investigated comparatively. The effect of Li⁺ ions on the luminescence properties of Dy³⁺ in α-Sr₂P₂O₇ host, including luminescence intensity, optimal doping concentration, concentration quenching mechanism, and decay behavior, was discussed in detail by considering the defect generation in α-Sr₂P₂O₇:Dy³⁺, the charge compensation of Li⁺ ions and the role of Li₂CO₃ as solid flux expected in phosphors. The obtained excitation and emission spectra indicate that these as-prepared phosphors can be excited by ultraviolet light and show white light emission due to the combination of the ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions of Dy³⁺ ions. The CIE chromaticity coordinates and color correlated temperature of Dy³⁺ emission in the phosphor α-Sr_2(1−2x)Dy_2xLi_2xP₂O₇ (x = 0.03) with optimal fluorescence intensity was also calculated. The present work could be helpful for understanding the effect of the charge compensator (e.g. Li⁺ ion) on the luminescent properties of phosphors with non-equivalent ion-displacement and the design of novel phosphors by efficiently taking advantage of charge compensator (e.g. Li⁺ ion).