Many phosphor hosts, for example, nitrides and sulfides, often face challenges such as hydrolysis and oxidation, limiting their application in phosphorconverted white light-emitting diodes (pc-LEDs). In this study, we developed a highly humidity-resistant yellow-green-emitting phosphor BaSi 6 N 8 O:Ce 3+ (BSNO:Ce 3+ ). The DFT calculations revealed a high Debye temperature (Θ D = 1159 K), indicating a rigid crystal structure that contributes to the photoluminescence thermal quenching resistance of BSNO. Furthermore, we observed a notable positional shift of Ce 3+ in the BSNO lattice, contributing to an unusual photoluminescence (PL) red shift compared to BSNO:Eu 2+ . Importantly, BSNO:Ce 3+ exhibited remarkable PL stability under harsh conditions, showing no degradation in water for 10 days and less than 10% intensity loss at elevated temperatures up to 773 K. We constructed a prototype white LED with a high color rendering index (R a = 92) by combining a 365 nm chip with BSNO:0.03Ce 3+ and commercial phosphors, demonstrating its potential for advanced pc-LED applications.