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Phosphors with a rigid and symmetrical structure are urgently needed. The alkali lithosilicate family (A[Li3SiO4]) has been extensively studied with a narrow emission band due to its unique cuboid-coordinated environment and rigid structure. However, here we demonstrate for the first time Ce-doped NaK2Li[Li3SiO4]4 phosphors with a broad emission band, a high internal quantum efficiency (85.6%), and excellent thermal stability. Photoluminescence indicates the Ce's preference to occupy the Na+ site, leading to a strong blue color emissio