We describe a series of fluorocarbon surfactant polymers designed for modifying fluorocarbon surfaces such as poly(tetrafluoroethylene). Novel fluorocarbon surfactant polymers poly(N-vinyldextranaldonamide-co-N-vinylperfluoroundecanamide), in which hydrophilic dextran oligosaccharides and hydrophobic perfluoroundecanoyl groups were incorporated sequentially onto a poly(vinylamine) backbone, were synthesized and characterized by FT-IR, NMR, and XPS spectroscopy. By adjusting the feed ratio of dextran to fluorocarbon branches, surfactant polymers with different hydrophilic/hydrophobic balances were prepared. The surface activity of the surfactants at the air/water interface was demonstrated by significant reductions in water surface tension. Surfactant adsorption and adhesion at the solid PTFE/aqueous interface were examined under well-defined dynamic flow conditions, using a rotating disk system. The surface activity at the air/water interface and adhesion stability on PTFE under an applied shear stress both increase with increasing density of fluorocarbon branches on the polymer backbone. The results show that stable surfactant adhesion on PTFE can be achieved by adjusting the hydrophilic dextran to hydrophobic fluorocarbon branch ratio.