Homopolymer of poly(perfluoroalkylethyl methacrylate) - CF3(CF2)(5)CH2CH2OCOCCH3CH2- (PFMA) was prepared by free-radical polymerization. Surface characterization of PFMA was performed by contact angle measurements and ESCA, The composition and structure of the outermost layer of the PFMA surface were analyzed. The outermost layer that primarily affects the surface properties of PFMA could be confirmed to consist of mainly perfluoroalkyl groups. Some of the ester groups of PFMA in the outermost layer were inferred to be exposed directly to the air : side, and it was suggested that the perfluoroalkyl groups in the outermost layer are arranged irregularly to the air side. Annealing can arrange the perfluoroalkyl groups to be more perpendicularly oriented at the polymer-air interface.