A poly(perfluoroalkylethyl methacrylate) and a series of poly(n-alkyl methacrylate) s such as poly(methyl methacrylate), poly(ethyl methacrylate), and poly(n-butyl methacrylate) were prepared and used to investigate the surface properties of polymer mixtures containing a fluorinated homopolymer and a nonfluorinated homopolymer and the effect of the sidechain length of poly(n-alkyl methacrylate) on the surface free energy for the polymer mixtures. Contact angles were measured for the surfaces of polymer mixtures by varying the concentration of poly(perfluoroalkylethyl methacrylate). From the contact angle data, it can be inferred that most of the poly(perfluoroalkylethyl methacrylate) added to poly(n-alkyl methacrylate) s is located in the outermost layer of polymer-mixture surface. Surface free energies for the outermost surfaces of polymer mixtures were calculated from the contact angle data using Owen and Wendt’s equation. The decrease in the surface free energy for the polymer mixture with the poly(perfluoroalkylethyl methacrylate) addition is more pronounced as the side-chain length of poly(n-alkyl methacrylate) decreases. Due to the steric effect of the side chain of poly(n-alkyl methacrylate), the arrangement of the perfluoroalkylethyl group of poly(perfluoroalkylethyl methacrylate) to the air side is considerably hindered. The ESCA analysis of atomic compositions of the surface for the polymer mixture verified that poly(perfluoroalkylethyl methacrylate) is preferentially arranged and concentrates at the polymer mixture-air interface. The results of functional group compositions obtained by ESCA showed that the functional group composition of -CF3 for the outermost layer has a more important effect on the surface free energy than that of -CF2- and confirmed the hindrance of the arrangement of perfluoroalkylethyl group to the air side by the side chain of poly(n-alkyl methacrylate).