The effects of solvents, fluorinated monomer content and film-formation methods on the surface structures of random copolymers composed of methyl methacrylate (MMA) and 2-perfluorooctylethyl methacrylate (FMA) were investigated by contact angle goniometry, X-ray photoelectron spectroscopy, sum frequency generation (SFG) vibrational spectroscopy and surface tension measurement. It is found that, with cyclohexanone as the solvent, there is a critical FMA content of 9 mol%, below which the copolymer films by spin coating have a more surface segregation extent of fluorinated moieties than those by solution casting; above which the copolymer films by solution casting have a more surface segregation extent of fluorinated moieties than those by spin coating. However, with toluene as solvent, the critical FMA content lowers down to 3 mol%. We believe that the solvent nature and the content of fluorinated moieties in the random copolymer have the great effect because the combined effect of these two factors can determine the random copolymer chain conformations and their thermodynamic dominating factors in the solution and at the solution-air interface. A thermodynamic analysis combining the entropic and enthalpic effects is suggested to explain the observed phenomenon. This research is believed to obtain an enhanced understanding of the surface formation mechanism of the polymer films and thus demonstrate how to promote the segregation of fluorinated moieties at the polymer film surfaces. (C) 2010 Elsevier Inc. All rights reserved.