A new strategy for the synthesis of a well-defined redox active polymer, a polyacrylate bearing TEMPO, and its grafting onto a gold substrate is described. It consists of polymerizing an acrylate bearing an alkoxyamine by RAFT, followed by aminolysis of the trithiocarbonate chain-end into a thiol that is exploited for the polymer grafting onto the gold sensor. Thermal activation of the alkoxyamine under air provides the redox polymer with a high yield. Its electroactivity is evaluated by a electrochemical quartz crystal microbalance (EQCM).