Low-voltage-operating, high-performance organic field-effect transistors (OFETs) play a critical role in the development of analog and digital integrated circuits for the next generation of electronics. To meet these demands, an OFET should possess specific characteristics, including a high dielectric constant (k) to increase capacitance for efficient field-effect charge, a hydrophobic surface to prevent charge trapping, and low leakage current to ensure stable operation. This study presents a novel approach to achieve high-k characteristics (>8) using robust polysilsesquioxane (PSQ)-based dielectrics. This approach involves inducing dipolar side-chain reorientation under an electric field, leading to low-voltage-driven OFETs with remarkable field-effect mobility levels, reaching up to 27 ㎠ V<SUP>-1</SUP>s<SUP>-1</SUP>. Various PSQs are examined, each exhibiting distinct polarization phenomena, resulting in different hysteresis behaviors during device operation. These materials enable the fabrication of printed unit devices on flexible platforms and integrated devices, demonstrating reliable switching and memory performance under low-voltage conditions. Therefore, this straightforward yet effective synthesis method for high-k PSQ dielectrics holds the potential to advance the development of practical, printable high-k dielectrics for organic electronics, ultimately contributing to the realization of nextgeneration integrated electronics.