We present the controlled radical polymerization of homo and block copolymers containing tert-butoxycarbonylaminomethyl acrylate (tBAMA) via ATRP. By varying monomer concentration, solvent, reaction temperature, and ligand (PMDETA, HMTETA, TPMA, Me6TREN and dNbpy), suitable reaction conditions could be established. Moderate control over the polymerization was achieved when using Me6TREN as ligand, whereas this could be drastically improved in case of dNbpy. For block copolymerization, a variety of macroinitiators (polystyrene, poly(n-butyl acrylate), poly(ethylene oxide)) were prepared via ATRP or end group modification. Block extensions resulted in well-defined block copolymers with moderately low dispersity indices (Mw/Mn = 1.12–1.36). In addition, the use of a bromine-functionalized porp core as multifunctional initiator (n = 4) resulted in monomodal star-shaped PtBAMA. The applied homopolymers, macroinitiators, and diblock copolymers were characterized by 1H NMR, 13C NMR and SEC—as well as MALDI–ToF f...