A broadband near-infrared (NIR) luminescence that is comparable to chromium ions activated materials is fulfilled in Li3Sc2(PO4)3:Fe3+ phosphor, which is highly desired for environmental and biomedical applications due to the non-toxicity of Fe3+ ions. Structural and spectral analysis reveal that the broadband NIR emission peaked at 805 nm with a full width at half-maximum of 130 nm is derived from the non-selective two-site occupation of Fe3+ in the Sc3+ sites. A high internal/external quantum efficiency of 53 %/38.7 % is achieved via relaxing the selection rule for the forbidden 4T1(4G) → 6A1(6S) transitions of Fe3+ by larger lattice distortion. The influence of Fe3+ concentration and environment temperature on the broadband NIR luminescence properties of the as-prepared phosphors are also investigated. Finally, a NIR pc-LED prototype is fabricated and its electro-optical performance has guaranteed the applications in non-destructive detection and night vision. All the results have validated Li3Sc2(PO4)3 as a novel matrix system for access to highly efficient broadband NIR Fe3+-doping phosphor materials.