<p>New generation of Cr³⁺-free eco-friendly phosphors (no risk of Cr³⁺ → Cr⁶⁺ oxidization toxicity) are highly sought to develop broadband NIR light sources. As an essential element for body health, Fe³⁺ ion would be an exceptional alternative in strong octahedral crystal field. Here, the Fe³⁺ activators were utilized in orthoborate-pyroborate A₂Sc₂B₄O₁₁ for creating novel NIR-emitting phosphors. A broad absorption over 240–450 nm due to O^2- → Fe³⁺ charge transfer transition was recorded for Sr₂Sc₂B₄O₁₁:Fe³⁺ (SSBO:Fe³⁺) at 370 nm and Ba₂Sc₂B₄O₁₁:Fe³⁺ (BSBO:Fe³⁺) at 355 nm. Resultant NIR emissions with large full width at half maximum about 170 nm were obtained for SSBO:Fe³⁺ peaked at 975 nm and BSBO:Fe³⁺ at 930 nm. The unique excitation of Fe³⁺ doping towards near-ultraviolet (near-UV) region was initially achieved for potential advantage of coupling a mainstream UV chip. Codoping of Yb³⁺ into A₂Sc₂B₄O₁₁:Fe³⁺ made emission peak red-shift towards 1000 nm and ~ 160-fold enhancement in the integral intensity owing to a robust energy extraction from the major dark (nonluminous) Fe³⁺. The optimized SSBO:0.02Fe³⁺,0.15Yb³⁺ exhibited considerable internal and external quantum efficiency ~ 78% and 48%, respectively. Compared to the luminescence thermal stability of ASBO:Fe³⁺ (32%@373 K, i.e., sustaining 32% of its room-temperature emission intensity at 373 K), the Yb³⁺ codoping endowed much superior stability &gt; 63%@373 K, and additional temperature sensing with relative sensitivity ~ 1.5% K⁻¹ at 423 K. Ultimately, by coating the novel phosphors onto UV ~ 365 nm chips, the home-made pc-LEDs were applied in night vision, food inspection, biomedical imaging, and spectroscopy analysis.</p>