Highly efficient phosphors are indispensable for near‐ultraviolet (n‐UV) pumped white light emitting diodes (WLEDs). In this work, a novel blue emitting Sr6GdSc(BO3)6:0.08Ce3+ phosphor was synthesized, exhibiting a broadband blue emission (full width at half‐maximum (FWMH) = 133 nm) excited by 375 nm. Furthermore, the blue emission of Sr6GdSc(BO3)6:0.08Ce3+ was enhanced by 3.9 times through codoping Na+ ions due to the influence of charge compensation and micromorphology and size of phosphor particles. At the same time, the internal quantum efficiency was improved from 45.4% to 98.6% and the external quantum efficiency up to 75.0%. Finally, the 365 nm excited two WLED devices were constructed by integrating Sr6GdSc(BO3)6:0.08Ce3+, Sr6GdSc(BO3)6:0.08Ce3+,0.08Na+, commercial green and red phosphors with high color rendering index. These results reveal that the phosphors have prospective application in high‐quality warm white lighting.