In recent years, organic photonic field-effect transistors have made remarkable progress with the rapid development of conjugated polycrystalline materials. Liquid crystals, with their smooth surface, defined layer thickness, and crystalline structures, are commonly used for these advantages. In this work, a series of smectic liquid crystalline molecules, 2,9didecyl-dinaphtho-thienothiophene (C10-DNTT), 2,7-didecyl-benzothienobenzothiopene (C10-BTBT), 3,9-didecyl-dinaphtho-thiophene (C10-DNT), and didecyl-sexithiophene (C10-6T), have been used in photonic transistor memory, functioning as both hole-transport channels and electron traps to investigate systematically the reasons and mechanisms behind the memory behavior of smectic liquid crystals. After thermal annealing, C10-BTBT and C10-6T/C10-DNTT are homeotropically aligned from the smectic A and smectic X phases, respectively. The 3D-ordered structure of these smecticaligned crystals contributed to efficient photowriting and electrical erasing processes. Among them, the device performance of C10-BTBT was particularly significant, with a memory window of 21 V. The memory ratio could reach 1.5 × 10 6 and maintain a memory ratio of over 3 orders after 10,000 s, contributing to its smectic A structure. Through the research, we confirmed the memory and light/bias-gated behaviors of these smectic liquid crystalline molecules, attributing them to reversible molecular conformation transitions and the inherent structural inhomogeneity inside the polycrystalline channel layer.