High-temperature negative thermal quenching (NTQ) phosphors are crucial to high-performance light-emitting devices. Herein, we report the high-temperature NTQ effect in deep-red to near-infrared (NIR) emitting copper iodide cluster-based coordination polymers as unconventional phosphors, whose NTQ operating temperature can reach as high as 500 K, the highest temperature reached by NTQ molecular-based materials.