ABSTRACT The integration of dynamic covalent bonds with photoswitches represents a rapidly advancing frontier in the development of dynamic covalent materials with photo‐adaptivity. We report the synthesis and characterization of three imine‐derived diarylethene photoswitches DAE1 ‐ DAE3 . All photoswitches demonstrate excellent photochromic performance. Notably, the nitro‐substituted photoswitch DAE1 exhibits rapid bidirectional response, a high ring‐closing quantum yield of up to 0.83, and ultrahigh photoconversion efficiency under visible light irradiation, achieving a photocyclization yield of 96% under violet light and a quantitative photocycloreversion yield under green light. Additionally, DAE1 displays great fatigue resistance and thermal stability. These photochromic compounds featuring dynamic imine bonds hold considerable potential for designing photo‐responsive constitutional dynamic systems.