Poly(2,2,6,6-tetramethyl-1-piperidinyloxy-methacrylate), or PTMA, has been widely employed in a number of applications, ranging from energy storage, oxidation catalysis, fluorescence quenching and biofouling. While its nitroxide moiety allows for a broad range of applications, polymerization techniques to create PTMA have not been synthetically diverse. Traditionally, radical polymerizations (i.e. classic and reversible-deactivation) have been the primary method to synthesize PTMA and more recently, an anionic polymerization method has been reported. Each of these methods offer a number of benefits while inherently introducing individual challenges, namely, the lack of molecular weight control and nitroxide content in PTMA when employing radical polymerization, the difficulty of introducing comonomers with a range of properties via anionic polymerization and the employment of environmentally challenging solvents in both. In this dissertation, each individual challenge is addressed through the development of two polymerization methods. In this thesis, an additive controlled method, employing a bulky, sterically hindered countercation complex is introduced. This method allows for the controlled polymerization of PTMA with a broad range of molecular weights and high nitroxide content. The controlled polymerization of partially fluorinated methacrylate monomers, which have been known to be particularly difficult to polymerize via anionic polymerization, is also achieved. Subsequently, block copolymers with poly(2,2,2-trifluoroethyl methacrylate) (PTMA-b-PTFEMA) are prepared via sequential monomer addition and their nanostructures in thin films are characterized. A number of applications have found limitations in their use of PTMA films due to its poor mechanical properties. The anionic polymerization developments are complimented with nanoindentation to characterize the mechanical properties of PTMA films and explore how they can be tuned by the incorporation of PTFEMA. Reversible-deactivation radical polymerization methods for poly(methacrylate)s, including PTMA, are also developed. In particular, an aqueous miniemulsion method, based on activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) is introduced. The methods developed allowed for the controlled polymerization of styrene and various methacrylates. The methods presented rely on water as solvent and afford increased environmentally friendliness due to their low-level metal catalyst usage and oxygen insensitivity. Finally, PTMA-containing amphiphilic random copolymers are synthesized via classic ATRP and are introduced as materials for marine fouling applications.