Coating Nitinol (NiTi) surfaces with a polymer layer has become very appealing in the past few years owing to its increased attraction in the biomedical field. Although its intrinsic properties helped ensure its popularity, its extensive implementation is still hampered by its nickel inclusion, making it sensitive to pitting corrosion and therefore leading to the release of carcinogenic Ni2+ ions. Among all recent ways to modify NiTi surfaces, elaboration of self-assembled monolayers is of great interest as their high order confers a reinforcement of the metal surface corrosion resistance and brings new functionalities to the metal for postmodification processes. In this work, we compare the electroassisted and thermally assisted self-assembling of 11-(2-bromoisobutyrate)-undecyl-1-phosphonic acid (BUPA) to the classical immersion process on NiTi surfaces initially submitted to a hydrothermal treatment. Among all tested conditions, the electroassisted grafting of BUPA at room temperature appears to be the most promising alternative, as it allows grafting in very short times (5-10 min), thus preventing its degradation. The thus-formed layer has been proven to be sufficient to enable the surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-(dimethylamino)ethyl methacrylate.