Sunlight-like full-spectrum phosphor-converted light-emitting diodes (pc-LEDs) require near-infrared (NIR) emission bands to fill the spectrum gap and consequently propel their widespread applications. Although fluoride NIR phosphors have been increasingly investigated, balancing high quantum efficiency (QE), high thermal stability, and wideband NIR emission to obtain excellent overall performance in a single system is still a challenge for Cr3+-doped fluoride NIR phosphor and is significant for direct utilization. Herein, a high-efficiency and thermally stable broadband NIR emission was realized in a novel LiSrGaF6:Cr3+ fluoride phosphor benefitting from a relatively weak crystal field and electron-phonon coupling effect. Upon blue light excitation, the ultra-broad NIR luminescence ranging from 650 to 1150 nm can be achieved with an FWHM of 149 nm peaking at ∼813 nm. Furthermore, this system possesses a high QE of up to 76.88% and its emission intensity at 423 K still maintains 61.62% of its initial intensity at room temperature. An NIR output power of 42.82 mW and photoelectric conversion efficiency of 14.27% of NIR pc-LED devices have also been presented based on this NIR phosphor, demonstrating its possible application in compact nonvisible light sources. In addition, a highly continuous sunlight-like vis-NIR pc-LED was further constructed by employing a blue chip with commercial cyan (BaSi2O2N2:Eu2+), yellow (Y3Al5O12:Ce3+), red (CaAlSiN3:Eu2+), and this LiSrGaF6:Cr3+ NIR phosphor. The as-obtained pc-LED exhibits an ultra-broad spectrum ranging from 400 nm to 1000 nm, exhibiting a higher color reproduction with a color rendering index (CRI) of 95.1 and luminous efficiency (LE) of 50.22 lm W-1. These results indicate that LiSrGaF6:Cr3+ phosphor can be a promising NIR phosphor candidate for high-quality sunlight-like full-spectrum lighting and infrared night vision technology.