The relationship between the adhesion of surfaces separated by a molecularly thin liquid film and the surface energy of the film was investigated. AFM-based force–distance curves were measured on a series of carbon surfaces coated with hydroxyl-terminated perfluoropolyether (PFPE) films. The surface energy of the PFPE films was varied by altering either the total film thickness or the bonding ratio of the film by changing the concentration of the PFPE film in the solution and/or the pull-rate during dip-coating. A linear relationship between adhesion force and surface energy was observed. Adhesion was found to vanish at non-zero values of surface energy. The experimental results indicate that the adhesive force between macroscopic bodies separated by molecularly thin liquid films is linearly proportional to the excess surface energy of the film.