ABSTRACT High‐emission coatings are the focus of significant attention for their efficient thermal protection in aerospace applications. Aluminum–chromium phosphate solution (ACP) was synthesized in this study by utilizing H 3 PO 4 , Al(OH) 3 , CrO 3, and CH 3 OH as raw materials. Subsequently, a room‐temperature curing high‐emissivity coating was effectively developed by employing ACP as the binder, Mg‐MOF‐74 as the curing agent, SiC and ZrB 2 as radiating agents, and Al 2 O 3 and ZrO 2 as high‐temperature stabilizers. Consequently, the coating exhibited exceptional thermal stability and radiation performance, with a mass residue rate of 98.71% after exposure to 1500°C. And the emissivity exceeded 0.93 at room temperature and measured ε (3–8 µm) = 0.84 and ε (8–18 µm) = 0.9 after treatment at 1200°C. Thus, the coating developed in this study provides durable and highly effective thermal protection under high‐temperature conditions.