We studied styrene and fluoroalkylfumarate (FAF) copolymers and their surfaces by means of contact angle measurement and X-ray photoelectron spectroscopy (XPS). The surfaces of the copolymers were very hydrophobic (even with a small amount of FAF) because of the concentration of FAF segments at the surface. The hydrolyzed surfaces of the copolymers became slightly hydrophilic compared to the as cast. The XPS data suggested that the fluoroalkyl groups seemed to be primarily hydrolyzed. The surfaces with a large amount of FAF changed their characteristics to hydrophobic again under atmospheric conditions. This phenomenon was due to the inversion of the carboxyl and the fluoroalkyl groups. These hydrolyzed surfaces seemed to be useful for modifying polymer surfaces by attaching to other functional molecules.