ABSTRACTPoly(itaconic acid) (PIA) was grown from surface-tethered initiator sites via atom transfer radical polymerization (ATRP). The surface-tethered PIA layers were grown from hydroxyl-terminated SAMs capped with initiator molecules of 4-(chloromethyl)-benzoylchloride. This polymerization initiator molecule and a copper-based organometallic catalyst allowed tethered PIA chains to be grown via ATRP at room temperature in aqueous solutions. Ellipsometric studies and external-reflection, Fourier-transform infrared spectroscopy (ER-FTIR) confirm the presence and growth of the surface-tethered PIA layer. We describe here how changing the temperature of polymerization alters the layer growth and kinetics of the process, and demonstrate, via ER-FTIR spectroscopy, that these surface-tethered layers do bind cationic dyes through ion-exchange mechanisms.