Abstract Over the past decade, molecular‐switch‐embedded memory devices, particularly field‐effect transistors (FETs), have gained significant interest. Molecular switches are integrated to regulate the resistance or current levels in FETs. Despite substantial efforts, realizing large memory window with a long retention time, a critical factor in memory device functionality, remains a challenge. This is due to the inability of an isomeric state of a molecular switch to serve as a stable deep trap state within the semiconductor layer. Herein, the study addresses this limitation by introducing chemical bonding between molecular switch and conjugated polymeric semiconductor, facilitating closed isomer of diarylethene (DAE) to operate as a morphologically stable deep trap state. Azide‐ and diazirine‐anchored DAEs are synthesized, which form chemical bonds to the polymer through photocrosslinking, thereby implementing permanent and controllable trapping states nearby conjugated backbone of polymer semiconductor. Consequently, when diazirine‐anchored DAE is blended with F8T2 and subjected to photocrosslinking, the resulting organic FETs exhibit remarkable memory performance, including a memory window of 22 V with a retention time over 10 6 s, a high photoprogrammable on/off ratio over 10 3 , and a high operational stability over 100 photocycles. Further, photophore‐anchored DAEs can achieve precise patterning, which enables meticulous control over the semiconductor layer structure.