AbstractCr3+‐activated near‐infrared (NIR) emitting phosphors are considered as one of the most potential light‐conversion materials for NIR phosphor converted light‐emitting diodes (NIR pc‐LEDs). However, it is still a challenge for a single Cr3+ ion to achieve a flat ultra‐broadband emission toward multi‐functional spectroscopy applications. Herein, a chemical unit co‐substituting strategy is utilized to regulate the crystallographic occupancy of Cr3+ ions, and a flat ultra‐broadband NIR emission is successfully realized with a record emission wavelength of 915 nm in garnet‐type phosphors Ca3Sc2‐xHfxAlxSi3‐xO12: yCr3+ (0 ≤ x ≤ 1, 0.02 ≤ y ≤ 0.06), together with a large full width at half maximum (FWHM) regulation from 130 to 250 nm. The relation between the site occupation of Cr3+ ions in disordered [CaO8], [(Sc, Hf)O6] and [(Si, Al)O4] polyhedrons and the corresponding NIR emission are clarified by carefully evaluating the structural evolution, Raman spectra, electron paramagnetic resonance and time‐resolved emission lifetime spectra of Cr3+ ions. The corresponding crystal field strength of Cr3+ ions is investigated to further clarify the multi‐sites induced flat broadband NIR emission. Finally, a blue light pumped NIR pc‐LED is fabricated with a total output power of 37.58 mW and photoelectric conversion efficiency (PCE) of 13.67%@100 mA, which realizes the multi‐functional applications in night vision imaging, non‐destructive detection and palmprint vein recognition for assistant medical treatment.