Recent advances in semiconductor performance afforded by organic π-electron molecules, carbon-based nanomaterials, and metal oxides have been a central scientific and technological research focus over the past decade for flexible and transparent electronics. However, recent advances in semiconductor require corresponding advances in compatible gate dielectric materials, which exhibit excellent electrical properties such as large capacitance, high breakdown strength, low leakage current density, as well as mechanical flexibility with arbitrary substrates. High-k inorganics such as hafnium dioxide (HfO2) or zirconium dioxide (ZrO2) offer some improvements in device performance, but these materials must be very thick to avoid leakage and are difficult to deposit as smooth films on plastics due to high process temperature. Conventional organic/polymeric materials are readily accessible and solution processable. However, these materials exhibit low capacitances, and the corresponding TFTs operate consequently at relatively high voltages. More recently, to combine the desirable properties of high-k metal oxides and organic dielectric processability and mechanical flexibility, a new approach for fabricating gate dielectrics using self-assembled multilayers has emerged. In this presentation, we introduce novel organic-inorganic hybrid gate dielectrics, fabricated by self-assembled multilayer deposition, and its application with unconventional semiconductors. We first present an overview of hybrid dielectric materials for thin-film transistor (TFTs). We next describe the design, fabrication, and applications of solution-deposited organic-inorganic hybrid multilayers, using self-assembly techniques which provide chemical bonding between organic-inorganic layers.