A photosensitive polyimide (PSPI) is synthesized to serve as the gate dielectric in organic thin-film transistors (OTFTs). A method to control the charge density within the channel of the OTFT using the PSPI on a silicon dioxide gate dielectric is proposed. The surface energy, surface carriers, and capacitance of gate dielectrics can be tuned by varying irradiation doses of UV light on the PSPI surface to create ultrahigh performance pentacene-based OTFTs with an average field-effect mobility (μ) of above 6.0 cm²/Vs. The correlation between the surface energy of the PSPI films and the μ value of OTFT devices is investigated. Moreover, the impact of gate-dielectric properties on the structural properties of pentacene films is closely related to the electrical characteristics of OTFTs. The results of contact angle, X-ray diffraction, electrostatic force microscopy, and micro-Raman spectroscopy measurements indicate that the surface energy and doping carriers coming from the PSPI film play important roles in the carrier transport of pentacene film for OTFT applications.