Inconsistency Between Photoluminescence and Persistent Luminescence in Sb3+/Mn2+ Co‐Doped Cs3Cd2Cl7

Persistent luminescence (PersL) materials have garnered significant attention in applications such as emergency signage, anti‐counterfeiting, and bioimaging. However, most inorganic PersL materials exhibit identical photoluminescence (PL) and PersL spectra. While organic materials can achieve PL‐PersL inconsistency, their short‐lived PersL times severely restrict practical implementation. This study reveals that Cs3Cd2Cl7:1%Sb3+,1%Mn2+ emits cyan PL and orange PersL, featuring a PersL time surpassing 3600 s. The discrepancy between the PL and PersL can be attributed to their different luminescent pathways. For PL, the primary pathway involves electronic relaxation from the excited state of Sb3+ to self‐trapped state, followed by radiative transition to the ground state. In contrast, PersL mainly involves the electrons released from traps migration to the conduction band, then to the Cl−‐Mn2+ charge transfer band, where they are transferred to the 4T1 energy level of Mn2+, followed by a radiative transition back to the 6A1 energy level. Finally, based on the unique PL‐PersL inconsistency characteristic of Cs3Cd2Cl7:Sb3+,Mn2+, this study demonstrates its application in dynamic anti‐counterfeiting and multi‐dimensional information encryption. This work provides a new strategy for developing ultra‐long PersL materials with PL‐PersL inconsistency.