Perovskite compounds are always the focus in the material research field. Herein, the polycrystalline samples and single crystals of Na2ZrTeO6, a B-site ordered double-perovskite compound, were prepared successfully. Single crystal X-ray diffraction demonstrated that Na2ZrTeO6 crystallizes in the cubic space group Fm-3m (No. 225) with unit parameters of a = b = c = 7.80360(10) Å. The crystal structure of Na2ZrTeO6, formed by ZrO6 and TeO6 octahedra through sharing the corner oxygen atoms, belongs to the typical rock-salt-type perovskite structure. The density functional theory calculations show that Na2ZrTeO6 has a direct band gap with band gap of 3.21 eV, which is lower than the experimental value of 3.85 eV. Interestingly, the powder samples of Na2ZrTeO6 exhibit a self-activated near-infrared emission centered at 780 nm under ultraviolet light excitation. And a strong luminescence thermal stability was also observed. Compared to room temperature, the luminescence intensity can maintain 64 % at 200 °C.