Near-infrared (NIR) luminescence materials with broadband emissions are necessary for the development of light-emitting diodes (LEDs) based light sources. However, most known NIR-emitting materials are limited by their low external quantum efficiency. This work demonstrates how the photoluminescence quantum efficiency of europium-activated calcium oxide (CaO:Eu) NIR phosphor can be significantly improved and stabilized at operating temperatures of LEDs. A carbon paper wrapping technology is innovatively developed and used during the solid-state sintering to promote the reduction of Eu3+ into Eu2+. In parallel, the oxygen vacancies in the CaO lattice are repaired utilizing GeO2 decomposition. Through this process, a record-high external quantum efficiency of 54.7% at 740 nm is obtained with a thermal stability greatly improved from 57% to 90% at 125 degrees C. The as-fabricated NIR-LEDs reach record photoelectric efficiency (100 mA@23.4%) and output power (100 mA @ 319.5 mW). This discovery of high-performance phosphors will open new research avenues for broadband NIR LED light sources in a variety of photonics applications.