Visible‐to‐near‐infrared (VIS‐NIR) luminescent materials are in great demand in the field of non‐destructive testing such as component determination and hyperspectral imaging. Although Cr3+‐activated phosphors are widely reported, controllable tailoring ultra‐wide VIS‐NIR luminescence excited by blue light is still a challenge. The strategies of cationic substitution and energy transfers are effective for adjusting the luminescence of Cr3+‐activated phosphors. In this work, a series of Cr3+‐doped Sc‐based solid solution phosphors (Ba3‐mSrmSc4O9:Cr3+) are reported. Under the excitation of blue light, these phosphors exhibit broadband emission due to the different luminescence centers induced by Cr3+ occupying different cationic sites. Because of the weaker crystal field strength, Cr3+ realizes a broadband emission with a longer peak position (λem = 820 nm) and broader full width at half maximum (FWHM≈182 nm) in Ba2SrSc4O9. Furthermore, Ce3+/Yb3+ ions are introduced into Ba2SrSc4O9:Cr3+, achieving an ultra‐wide VIS‐NIR luminescence (460–1200 nm) by the Ce3+→Cr3+→Yb3+ multiple energy transfers. Designing energy transfers is beneficial to improve the quantum efficiency and weaken the thermal quenching. Finally, the NIR phosphor‐converted light‐emitting diode (pc‐LED) fabricated by Ba2SrSc4O9:Cr3+ demonstrates great potential in night‐vision and water component detection. This work provides an effective design idea for controllable tailoring ultra‐wide VIS‐NIR luminescence by chemical substitution and energy transfer.