We improved the performance of pentacene-based thin film transistors by changing the curing environment of poly(4-vinylphenol) (PVP) gate dielectrics, while keeping the dielectric constant the same. The field-effect mobility of the pentacene TFTs constructed using the vacuum cured PVP was higher than that of the device based on the Ar flow cured gate dielectric, possibly due to the higher crystalline perfection of the pentacene films. The present results demonstrated that the curing conditions used can markedly affect the surface energy of polymer gate dielectrics, thereby affecting the field-effect mobility of TFTs based on those dielectrics.