In this work, we synthesized novel hybrid nanostructures, featuring polymer nanodot-embedded alkyl silicon oxide (ASiO) networks, by two-step (sol-gel and thermal cross-linking) reactions between poly(4-vinylphenol) (PVP) and triethoxyvinylsilane (or vinyltriethoxysilane - VTES). The resulting cross-linked ASiO hybrids embedded with PVP nanodots (nanoparticles) (X-ASiO-PVPNP) were employed as a thermally stable memory layer for the TOMDs with the poly(3-hexylthiophene) (P3HT) channel layers. The hybrid TOMDs could be operated at low voltages (1~5 V) and exhibited outstanding operation stability at high temperatures (150 °C) due to the pronounced hysteresis by the PVP nanodots and the high thermal stability by the cross-linked VTES-derived ASiO network structures.