Adsorption of well-defined fluorinated polymers onto clinically relevant poly (tetrafluoroethy lene) (PTFE) substrates offers an attractive method for modifying the surface properties of chemically inert PTFE. Reversible addition-fragmentation chain transfer (RAFT) was successfully used for synthesis of the polymers in this study: the homopolymers poly(2,3,4,5,6- pentafluorostyrene) (PFS), poly(2,2,3,3-tetrafluoropropyl acrylate) (FTFPA), and poly(2,2,3,3-tetrafluoropropyl methacrylate) (PTFPMA) as well as their block copolymers with feri-butyl acrylate (tBA). Watersoluble blocks were synthesized through the hydrolysis of the i-butyl side groups of P( tBA) to the corresponding carboxylic acid. Adsorption of selected polymers onto PTFE from a series of solvents (methyl ethyl ketone (MEK), dimethylformamide (DMF), fluorobenzene (FB), dichloromethane (DCM)) was investigated using X-ray photoelectron spectroscopy (XPS) and sessile water drop measurements. The three homopolymers studied all adsorbed irreversibly (i.e., were not removed by washing) from organic solvents at ambient temperature. PFS displayed the highest adsorption, and was attributed to strong hydrophobic interactions. From angle-resolved XPS it was concluded that PFS became impregnated into the PTFE substrate down to depths of 100 Å when using FB as a solvent. The carboxylic acid-containing block copolymers adsorbed more effectively from DMF (a good solvent for the poly(acrylic acid) block) compared to MEK. The resulting modified PTFE substrates displayed high stability with respect to desorption in aqueous solution, yet conformational changes of the adsorbed polymer resulted in a switchable hydrophobic-hydrophilic surface (in air or water, respectively). These results highlight the success of a facile and simple approach to irreversibly adsorb functional polymers to a nonfunctional fluorinated surface.