This work is the first to synthesize the red-emitting Li3Bi3Te2O6 phosphors using the conventional high-temperature solid-state reaction. The phase purity, particle morphology, and luminescent properties are analyzed in detail. Upon the near-ultraviolet (n-UV) excitation on 395 nm, Li3Bi3Te2O6:Eu3+ phosphors show four emission peaks due to 5D0 → 7FJ (J = 1, 2, 3, 4) transitions and the strongest peak is at 610 nm (5D0 → 7F2). The best doping concentration of Eu3+ ions is found to be 0.45 mol. The critical transfer distance (Rc) of the energy transfer between the Eu3+ ions reaches 11 A and the luminescence quenching is confirmed by the nearest-neighbor ions interaction. The commission international de l'Eclairage (CIE) chromaticity coordinates (0.655, 0.344) of Li3Bi3Te2O6:0.40Eu3+ phosphors are in the red region. The values of decay time are calculated in the millisecond time range from 0.878 to 0.493 ms. Phosphors show common thermal stability with activation energy (0.25 eV). All the properties indicate that Li3Bi3Te2O6:Eu3+ phosphors have potential applications in displays and photonic devices.