a rapid development and now become the preferred white light sources for general illumination and backlight display. [1] Near-infrared (NIR) pc-LEDs were accordingly proposed as a new-generation light source to circumvent the limitations of the application of conventional counterparts like NIR semiconductor LEDs, supercontinuum lasers and halogen lamps to compact optical systems. [2] Especially, NIR pc-LEDs covering a wide spectral range of 700-1100 nm, when coupled with Si-based photodetectors, can miniaturize NIR spectroscopy to be an integrated module for mobile phones and smart wearables, thereby realizing instant identification of food, clothing and pharmaceuticals, and real-time monitoring of human health. [3] However, the spectral properties and optical output power of NIR pc-LEDs are still far from practical application for the lack of satisfactory NIR phosphors.Phosphors play a key role in the conversion of narrowband blue light from LED chips to the desired broadband NIR one. Over the past few years significant effort has been devoted to exploiting a variety of ions including Cr 3+ , [4][5][6][7] Mn 2+ , [8] and Eu 2+[9] as the broadband NIR emitters, but only Cr 3+ has hitherto exhibited high internal quantum efficiency (IQE) and good photoluminescence (PL) thermal stability in a handful of host crystals, such as Gd 3 Sc 1.