In this work, a series of BaSrGd4O8:xBi3+ blue phosphors was synthesized employing the high-temperature solid-state method. Phase purity of the samples was verified by X-ray diffraction and Rietveld refinement. Time-resolved photoluminescence spectra revealed the existence of two distinct Bi sites. Subsequent optimization of dopant types and doping levels in the batch led to an almost twofold increase in quantum efficiency. The introduction of Eu3+ into the phosphors facilitated the construction of an energy transfer pathway. As the concentration of Eu3+ was increased, the emission color changed from blue to purple and finally to red. In addition, the thermal stability and potential applications of the phosphors were extensively investigated. Finally, two WLED devices were successfully fabricated with color rendering indices of 96.27 and 92.18, and correlated color temperatures of 5198 and 2475 K. This underscores the prospective application of these phosphors in the field of high-quality warm WLEDs.