Owing to the conventional phosphor-converted white LEDs (pc-WLEDs) generally suffer from blue-green cavity, thus, developing an appropriate phosphors covering both the blue and green regions in their emission spectra are very urgent. Herein, a novel Sc silicate phosphor, KBaScSi2O7:Eu2+ (KBSS:Eu2+), has been successfully designed and prepared via a solid-state reaction. The crystal structure, luminescent properties, thermal quenching, quantum efficiency as well as its application in UV-pumped WLEDs have been investigated systematically. The KBSS:Eu2+ phosphor exhibits a strong and broad excitation band ranging from 290 to 450 nm, and gives a sufficient cyan emission of 488 nm with a full-width half-maximum (FWHM) of 70 nm, which filled the blue-green cavity. Importantly, the optimized KBSS:Eu2+ phosphor possesses an ultrahigh quantum efficiency (QE) up to 91.3% and an excellent thermal stability retaining 90% at 423 K with respect to that measured at room temperature. Finally, the as-fabricated UV-based WLEDs device, with only coupled the mixture of KBSS:Eu2+ cyan phosphor and CaAlSiN3:Eu2+ red ones to a commercial 365nm UV chip, exhibits a satisfactory color-rendering index (Ra = 88.6), correlated color temperature (CCT = 3770K), and luminous efficiency (LE = 21 lm/W).