AbstractBroadband near‐infrared (NIR) emitting materials have gained considerable attention for their applications in lighting, displays, sensing, bio‐imaging, and optical amplification. Recently, numerous excellent broadband NIR emitting materials are developed by introducing Cr3+, Bi+, or Ni2+ ions to various hosts. However, there is a notable absence of reports on ultra‐broadband NIR emitters spanning the entire telecommunication window as well as the NIR‐I (700–1000 nm) and NIR‐II (1000–1700 nm) biological windows activated by vanadium ions. Herein, the study presents, for the first time to the best of the knowledge, ultra‐broadband NIR emission ranging from 850 to 1600 nm (peaking at ≈1000 nm) at room temperature in vanadium‐doped phosphate glass. Detailed spectra and microscopic structure analysis reveal that two V3+‐emitting centers predominantly contribute to the ultra‐broadband emission, corresponding to 3T2(3F)→3A2(3F) spin‐allowed and 3T2(3F)→1E(1D) spin‐forbidden electron transitions of tetrahedrally coordinated V3+ ions. Notably, the tunability of NIR emission peak is demonstrated by adjusting the local glass structure or the vanadium doping content. Moreover, glass‐converted light‐emitting diodes (gc‐LEDs) are fabricated from vanadium‐doped glass, and the potential applications are demonstrated. The work opens new avenues for the design and fabrication of broadband NIR‐emitting materials and opto‐electronic devices.