A chemically coupled polymer layer is introduced onto inorganic oxide dielectrics from a dilute chlorosilane-terminated polystyrene (PS) solution. As a result of this surface modification, hydrophilic-oxide dielectrics gain hydrophobic, physicochemically stable properties. On such PS-coupled SiO2 or AlOx dielectrics, various vacuum-and solution-processable organic semiconductors can develop highly ordered crystalline structures that provide higher field-effect mobilities (mu S-FET) than other surface-modified systems, and negligible hysteresis in organic field-effect transistors (OFETs). In particular, the use of PS-coupled AlOx nanodielectrics enables a solution-processable triethylsilylethynyl anthradithiophene OFET to operate with mu(FET) similar to 1.26 cm(2) V-1 s(-1) at a gate voltage below - 1 V. In addition, a complementary metal-oxide semiconductor-like organic inverter with a high voltage gain of approximately 32 was successfully fabricated on a PS-coupled SiO2 dielectric.