Eu 3+ -doped triple tellurium double perovskites LiBaLa [TeO 6 ], NaBaLa [TeO 6 ], LiBaBi [TeO 6 ] and NaCaBi [TeO 6 ] were synthesized by the general high temperature solid-state reaction. The crystal phase formations and morphology of the phosphates were confirmed by X-ray powder diffraction (XRD) and scanning electron microscope (SEM) measurements, respectively. The luminescence properties, including the photoluminescence (PL) excitation and emission spectra, decay curves (lifetimes), the color coordinates and the internal quantum efficiency (QE) were investigated. Eu 3+ -doped LiBaLa[TeO 6 ], NaBaLa[TeO 6 ], and LiBaBi[TeO 6 ] show the dominated electric dipole transition 5 D 0 → 7 F 2 with a pure red luminescence color and a fast decay. However, Eu 3+ -doped NaCaBi[TeO 6 ] presents the dominant reddish-orange emission from magnetic dipole transition 5 D 0 → 7 F 1 and a longer luminescence lifetime. The different luminescence features were discussed on the base of crystal structure, where Eu 3+ ions have two possible substitutions on A or B sites in double tellurium perovskites.ABO 3 compounds with perovskite structure are the most studied ferroelectric materials in the past years. 1-6 This well-known structure has a three-dimensional corner-sharing network of BO 6 octahedra with a large A-cation cavity occupying the AO 12 cuboctahedral. It is an important way to obtain high density samples with near optimal piezoelectric properties by doping rare earth ions (RE) in perovskites. 7 This brings another important research topic for perovskites, i.e., the luminescence properties. RE-doped perovskites as Eu 3+ -doped CaTiO 3 , 8,9 BaZrO 3 , 10 PbTiO 3 , 7 etc, have promising applications in luminescence and displays. [11][12][13] The great flexibility of A and B sites in ABO 3 allows very rich substitutions. This induces a large number of isotopic compounds with perovskite structure such as double perovskite oxides with a general formula A 2 B B O 6 in which B O 6 and B O 6 octahedra are corner-shared alternately. This framework forms cube-octahedral cavities filled by A-site cations. 14,15 Eu 3+ -doped double perovskite oxides have been given great attentions because of the possible applications as luminescence materials such as MgTiO 6 :Eu 3+ , 23 A 2 CaMoO 6 (A = Sr, Ba), 15 A 2 CaWO 6 (A = Sr, Ba) and Sr 1.9−x Ba x Eu 0.05 Li 0.05 MoO 6 (x = 0-1.9). 24 Eu 3+ -doped double perovskites have a broad excitation band ranging from ultraviolet to visible light region, and show efficient red luminescence. The studies have shown that the emission intensity of Eu 3+ -doped Sr 2 CaMoO 6 is 1.5 times higher than that of commercial Y 2 O 2 S:Eu 3+ ; 15 Sr 1.5 Eu 0.05 Li 0.05 Ba 0.4 CaWO 6 has 4.5 times stronger luminescence intensity than that of commercial red phosphor (Nichia) under 465 nm excitation. 24 In this study, new red-emitting phosphors of Eu 3+ -doped tellurium perovskites LiBaLa[TeO 6 ], NaBaLa[TeO 6 ], LiBaBi[TeO 6 ] and NaCaBi[TeO 6 ] were synthesized by the conventional high temperature solid state reac...