Surfaces of poly (fluoroalkyl methacrylate)s and poly (fluoroalkyl α-fluoroacrylate) s were investigated by measuring critical surface tension of wetting (γc). Thin layers of polymer films were obtained by the solvent casting method. The concentration of fluorine in the films was determind by Electron Spectroscopy for Chemical Analysis (ESCA). We observed a good relationship between the concentration of fluorine determined by ESCA spectra and γc of the thin polymer film.i. e., the more of the F1s ESCA signal, the less γc of the polymer film. It was concluded that the structure of either main chain and side chain fluoroalkyl group or the alkyl chain length of polymers affect the values of γc of the polymer films.