The self-organisation of semifluorinated segments was used to create polymers and block copolymers with ultra-low surface free energy. The aromatic polyester poly(p-phenylene oxydecyl-perfluorodecyl-isophthalate) showed an extremely low value of Y_sv of 9mN/m. It was proven that this low value was caused by an ordered surface structure. Introduction of these semifluorinated polyester segments into block copolymers with a basic structure (A-B)_n resulted in a combination of good filmforming properties of polysulfone with the low surface free energy of the semifluorinated polyester. Thus, materials were obtained having both good mechanical performance as well as anti-adhesion properties. The block copolymers can be used to prepare blends with the respective homopolymers with different degrees of phase separation. The polymers and block copolymers can form a self-cleaning surface when coated on roughened aluminium substrates. It was shown that the adsorption of proteins, such as human serum albumin and fibrinogen from buffer solutions, significantly decreased on such polymer surfaces.