Fluorinated hybrid materials were synthesized for a solution-processable gate insulator. The surface energy was modified by perfluoroalkyl chains contained in the hybrid gate insulator itself. We investigated the initial morphology and growth mode of pentacene and the characteristics of organic thin-film transistors (OTFTs) to determine how these characteristics depend on the surface energy. Pentacene growth was changed from a layer-by-layer mode to a three-dimensional (3D) island growth mode at low surface energy. Tightly and uniformly grown pentacene grains at 3D island mode induced good OTFT performance, but the carrier mobility was degraded at very low surface energy due to the large amount of grain boundaries.