AbstractAntimony (III)‐containing halide hybrids possess a distinctive stereoactivity with a 5s2 lone pair, which further induces significant structural distortions upon light excitation. Herein disordered dis‐[TPPen]2SbBr5 (TPPen = triphenylpentylphosphonium) and ordered ord‐[TPPen]2SbBr5, have been synthesized and exhibit self‐trapped excitons (STEs) emissions in the red‐to‐near infrared (NIR) range. Benefiting from a high distortion degree of STEs confined within the [SbBr5]2− unit and the pronounced alterations in the Sb─Br bond lengths upon blue‐light excitation, dis‐[TPPen]2SbBr5 achieves a greater level of excited state distortion and a larger Stokes shift than those of ord‐[TPPen]2SbBr5. The fabrication of blue light excited NIR light‐emitting device based on dis‐[TPPen]2SbBr5 demonstrates the prospective application in night vision supplemental lighting and non‐destructive examination. This work provides valuable molecular design strategies for the NIR luminescent materials in hybrid metal halides.