sources represented by halogen lamps, such as high energy consumption, short lifetime, and large heat release, and show huge application potential in agriculture, food, and bioimaging fields. [1] The pivotal long-wavelength Cr 3+ -activated NIR phosphors for NIR pc-LEDs are heavily dependent on expensive Sc-and In-based compounds. [2] LiScGeO 4 is a typically long-wavelength NIR phosphor with peak wavelength of 1120 nm and full-width at half-maximum (FWHM) of 300 nm. [3] The fabricated NIR pc-LED can check the file level of opaque items due to its high penetrating power ability. The emission peak is turned from 970 to 1020 nm, and FWHMs are broadened from 225 to 285 nm in (Li,Na)In 2 SbO 6 :Cr 3+ by substituting Li + with Na + , the NIR pc-LED has the merit of avoiding red storms. [4] Unfortunately, the low thermal stability and high cost are a brake on the practical application. Simultaneously, the characteristics of Cr 3+ -doped NIR phosphor in UV and visible (Vis) light absorption bands make it impossible to realize short-wavelength emission, neglecting the demand of ultra-wide Vis-NIR luminescent materials for nondestructive Cr 3+ -activated broadband near-infrared (NIR) phosphors, featured by the octahedral coordination preference and strong absorption in visible (Vis) region, have great potential application in nondestructive assessment. It is still a challenge to develop Cr 3+ -doped phosphors with the tetrahedrally coordinated Cr 3+ NIR emission behavior and ultra-wide Vis-NIR luminescence.