[en] More recently, Ce³⁺ activated γ-Ca₂SiO₄ has been reported and it shows great potential application as a yellow-emitting phosphor for white LEDs. However, β-Ca₂SiO₄, another known phase of Ca₂SiO₄, doped with Ce³⁺ is not available. It is interesting to know if β-Ca₂SiO₄:Ce³⁺ can also be suitable for white LEDs. For this reason, we synthesized a series of β-Ca₂SiO₄:Ce³⁺ phosphors by solid state reaction. β-Ca₂SiO₄:Ce³⁺ exhibits an intense blue emission band peaked at 425 nm with a bandwidth of 68 nm which is attributed to the typical Ce³⁺ 4f⁰5d¹→4f¹ transitions. The integral intensity of the concentration-optimized β-Ca₂SiO₄:Ce³⁺ can be as high as 71% of the commercial BAM blue phosphor upon 360 nm excitation. The excitation spectra of β-Ca₂SiO₄:Ce³⁺ consist of three broad bands with maxima at 252, 289 and 348 nm , which are ascribed to the 4f¹→4f⁰5d¹ transitions of Ce³⁺. Thermal quenching property of β-Ca₂SiO₄:Ce³⁺ was evaluated and the results show that the integral PL intensity at 150 °C maintains about 93% of that at room temperature. The excellent thermal stability and intense emission upon NUV light excitation suggest that β-Ca₂SiO₄:Ce³⁺ can be used as a potential blue-emitting phosphor for NUV white LEDs. - Highlights: • The photoluminescence properties of β-Ca₂SiO₄:Ce³⁺, Li⁺ were investigated. • It can be efficiently excited by NUV light. • It presents excellent thermal stability. • An intense blue-emitting silicate phosphor for white LEDs was obtained