In this study, we design and synthesize a novel photosensitive polyurethane material as a functional dielectric layer, which can adjust the crystallization of para-hexaphenyl (p-6P). The novel polymer is synthesized with a new monomer 2,2-bis(hydroxymethyl)butyl 4-cyanobenzoate (HM-4-CB), which contains benzene to provide crystal nucleus sites. The grain size and density of the p-6P crystal can be controlled by the content of HM-4-CB in the polymer structure. Therefore, this method can be used to regulate the grain size of semiconductor crystals and then to change the carrier mobility of the device. The results illustrate that with a suitable grain size of the p-6P semiconductor, excellent performance in terms of charge carrier mobility can be obtained.