A new range of end‐functionalized poly(1,1,2,2‐tetrahydroperfluorodecyl acrylate)s was synthesized by ATRP. Such macromonomers were used as reactive and steric stabilizers for the preparation of original core‐shell polyurethane particles in supercritical carbon dioxide. The nature of the chain end functionality, as well as the molar mass of the reactive stabilizer, were varied in order to investigate the role of such parameters on the properties of the resulting materials. Due to the low surface energy of PFDA combined with the high surface roughness induced by the specific microstructure of particles deposited on a silica plate, PUR materials exhibited super‐hydrophobic behavior with a water CA above 150°.magnified image