Wearable biosensing and food safety inspection devices with high thermal stability, high brightness, and broad near-infrared (NIR) phosphor-converted light-emitting diodes (pc-LEDs) could accelerate the next-generation NIR light applications. In this work, NIR La3–xGdxGa5GeO14:Cr3+(x= 0 to 1.5) phosphors were successfully fabricated by a high-temperature solid-state method. Here, by doping Gd3+ions into the La3+sites in the La3Ga5GeO14matrix, a 7.9-fold increase in the photoluminescence (PL) intensity of the Cr3+ions, as well as a remarkably broadened full width at half-maximum (FWHM) of the corresponding PL spectra, is achieved. The enhancements in the PL, PLE intensity, and FWHM are attributed to the suppression of the nonradiative transition process of Cr3+when Gd3+ions are doped into the host, which can be demonstrated by the decay curves. Moreover, the La1.5Gd1.5Ga5GeO14:Cr3+phosphor displays an abnormally negative thermal phenomenon that the integral PL intensity reaches 131% of the initial intensity when the ambient temperature increases to 160 °C. Finally, the broadband NIR pc-LED was fabricated based on the as-explored La1.5Gd1.5Ga5GeO14:Cr3+phosphors combined with a 460 nm chip, and the potential applications for the broadband NIR pc-LEDs were discussed in detail.