The (Ba,Ca)ScO2F:Bi3+,K+ phosphor with narrow emission band and green emission color peaking at 510 nm is demonstrated in the study. This phosphor is prepared using a solid-state reaction at high temperatures. Based on characterizing data, the increasing concentration of Ca2+ induces the shrinkage of the unit cell and the narrower spacing, leading to the increase in the photoluminescence of the phosphor. This also cause a red shift in the emitting range from 504 nm to 510 nm. The phosphor shows good absorption peaking at 415 nm, matching the excitation wavelength of the used nearultraviolet (UV) light emitting diode (LED) chip. When being applied in a white light‐emitting diodes (WLED) with 4,000 K, the phosphor could increase the luminous flux as its doping concentration increase. Besides, the WLED doping (Ba, Ca) ScO2F: Bi3+, K+ shows emission regions in blue, green, and red wavelength bands. The data from the study indicates that the phosphor is potential for developing the white-LED for backlight purposes.