A series of novel single-phase color tunable LiGd(WO₄)₂(LGW):Re³⁺ (Re = Tm, Tb, Dy, Eu) phosphors have been synthesized by a solid-state reaction. X-ray diffraction (XRD), FT-IR, photoluminescence (PL) and fluorescence decay curves were utilized to characterize the as-prepared samples. Under the excitation of UV light, LGW:Tm³⁺, LGW:Tb³⁺, LGW:Dy³⁺ and LGW:Eu³⁺ exhibit the characteristic emissions of Tm³⁺ (blue), Tb³⁺ (green), Dy³⁺ (yellow) and Eu³⁺ (red), respectively. On the one hand, by simply adjusting the doping concentration of Eu³⁺ ions in the LGW:2% Tm³⁺, 4% Tb³⁺, x% Eu³⁺ system, a white emission in a single-phase was achieved by blending simultaneously the blue, green, and red emissions of Tm³⁺, Tb³⁺, and Eu³⁺ ions in the LGW host, in which the energy transfer from Tb³⁺ to Eu³⁺ ions was found to play an important role. On the other hand, a white emission can also be realized based on the energy transfer from Tm³⁺ to Dy³⁺ ions in the LGW:2% Tm³⁺, x% Dy³⁺ system. The energy transfer mechanism from Tm³⁺ to Dy³⁺ ions has been demonstrated to be through dipole–quadrupole interaction and the critical distance (R_Tm–Dy) calculated by the concentration quenching method is 16.03 Å. The PL properties of as-prepared materials indicate that LGW:Re³⁺ (Re = Tm, Tb, Dy, Eu) may be potentially applied as single-phase white-light-emitting phosphors for UV-excited WLEDs.