The technology of solid-state lighting has developed for decades in various industries. Phosphor, as an element part, determines the application domain of lighting products. For instance, blue and red-emitting phosphors are required in the process of plant supplementing light, arrow-band emitting phosphors are applied to backlight displays, etc. In this work, a Bi3+-activated blue phosphor is obtained in a symmetrical and compact crystal structure of Gd3SbO7 (GSO). Then, the co-doping strategy of alkali metal ions (Li+, Na+, and K+) is used to optimize the performance. The result shows that the photoluminescence intensity is increased by 2.1 times and 1.3 times respectively by introducing Li+ and K+ ions. Not only that, it also achieves narrow-band emitting with the full width of half-maximum (FWHM) reaching 42 nm through Na+ doping, and its excitation peak position also shifts from 322 to 375 nm, which can be well excited by near-ultraviolet (NUV) light emitting diode (LED) chips (365 nm). Meanwhile, the electroluminescence spectrum of GSO:0.6 mol%Bi3+,3 wt%Na+ matches up to 93.39% of the blue part of the absorption spectrum of chlorophyll a. In summary, the Bi3+-activated blue phosphor reported in this work can synchronously meet the requirements of plant light replenishment and field emission displays.