Traditional lighting methods have environmental and efficiency drawbacks. These methods are gradually being overshadowed by light-emitting diodes (LEDs) because of their superior color rendering and energy efficiency. In this study, color-tunable NaBa2(Ba/Sr/Ca)Si2O7F:Eu2+ phosphors are successfully designed by modulating the local crystal field environment through homodominant-group cation substitution, thereby allowing for a spectral shift from blue to bright cyan. Detailed structural analysis of the samples demonstrated the synthesis of high-quality solid-solution materials. A comprehensive examination of the phosphor crystal structure, photoluminescence properties, and fluorescence lifetime reveal that the cyan phosphor possesses a remarkable internal quantum efficiency (IQE = 93%) and low thermal quenching characteristics (I423 K/I303 K = 84%). The results illustrate the critical role of Eu2+-activated cyan phosphors in reducing the spectral gap to attain a natural white-light spectrum, which is indispensable for achieving high color fidelity. The practical application of cyan phosphors in the fabrication of high-performance white LED (WLED) (Ra = 96.8) and fingerprint detection is validated, demonstrating their extensive utility in enhancing visual accuracy and identification.