The aim of this work was to investigate the degradation of the anti-adhesive properties of protective PTFE films during the hot embossing of thermoplasts, and to identify possible failure causes which reduce the lifetime of these films. A comparative XPS study of different deposited films and embossing parameters resulted in a better understanding of the film/polymer interactions at high temperatures. The loss of fluorine was found to be a major cause of the film quality degradation. It resulted from the diffusion of fluorinated entities or small polymer chains from the film to the embossed material during the embossing process. This led us to make some suggestions for the optimization of the working parameters in the hot embossing technique.