The effect of surface molecular motion on the wetting behavior of water on the thin film surfaces of poly(fluoroalkyl methacrylate)s with various fluoroalkyl (R-f) groups [PFMA-C-y; y: fluoromethylene number in R-f groups, y = 1, 2, 4, 6, and 8] was characterized, The receding contact angle of PFMA-C-y with short R-f groups (y = 1, 2,4, and 6) was larger than that of poly(fluoroalkyl acrylate) with short R-f group, [PFA-C-y, y <= 6]. This stable hydrophobicity observed for PFMA-C-y is due to tile restriction of thermal molecular motion by tile alpha-methyl group. Wide-angle X-ray diffraction (WAXD) and grazing incidence WAXD measurements revealed that tile R-f groups [PFMA-C-y, y <= 6] were not crystallized. PFMA-C-8 showed high advancing and receding contact angles due to the crystallization Of fluoroalkyl groups at the surface region. The hydrophobicity of PFMA-C-8 was improved after annealing due to the ordering of fluoroalkyl groups.