AbstractSummary: Three smectic poly(styrene‐b‐perfluorooctylethyl acrylate) block copolymers (S‐b‐AF8) with different degrees of polymerization (n, m) of the relative blocks were synthesized by atom transfer radical polymerization (S, n = 25; AF8 m = 2, 6, 23). The mesophase structure and transition temperatures were investigated by DSC and WAXD. The block copolymer having the shortest fluorinated block was blended with a thermoplastic elastomer SEBS in different proportions, in order to look at the effect of a further dilution of the perfluorinated groups on non‐wetting properties. Thin films of the block copolymers as well as the blends exhibited large contact angles with both water and n‐hexadecane, which resulted in low solid surface tensions. XPS findings at different photoemission angles confirmed the effective surface segregation of the mesogenic chains of the fluorinated polymer block.