This study introduces a novel strategy to achieve high-temperature phosphorescence (HTP) using planar rigid molecules as guests and rigid polymers as host matrices. The planar configuration of the guest molecules minimizes thermal vibration at high temperatures, while the rigid matrix further enhances the HTP performance. The doped materials exhibit an afterglow of 40 seconds at 293 K, 20 seconds at 373 K, 6 seconds at 413 K, and 1 second at 433 K. The study also explores the influence of rotational groups on the HTP performance, finding that as the rotational ability of the groups increases, the HTP performance decreases. Additionally, the materials are tested for their potential use in identifying rescue workers and trapped individuals in fires, demonstrating their effectiveness in high-temperature and thick-smoke environments. The twofold rigidity strategy, involving both the guest and host, is shown to be universally applicable, as demonstrated by the successful synthesis of HTP materials with other planar rigid molecules. This work paves the way for the development of organic HTP materials with broader applications.This study introduces a novel strategy to achieve high-temperature phosphorescence (HTP) using planar rigid molecules as guests and rigid polymers as host matrices. The planar configuration of the guest molecules minimizes thermal vibration at high temperatures, while the rigid matrix further enhances the HTP performance. The doped materials exhibit an afterglow of 40 seconds at 293 K, 20 seconds at 373 K, 6 seconds at 413 K, and 1 second at 433 K. The study also explores the influence of rotational groups on the HTP performance, finding that as the rotational ability of the groups increases, the HTP performance decreases. Additionally, the materials are tested for their potential use in identifying rescue workers and trapped individuals in fires, demonstrating their effectiveness in high-temperature and thick-smoke environments. The twofold rigidity strategy, involving both the guest and host, is shown to be universally applicable, as demonstrated by the successful synthesis of HTP materials with other planar rigid molecules. This work paves the way for the development of organic HTP materials with broader applications.