The Cu(0)-mediated reversible deactivation radical polymerization of N,N'-dimethylaminoethyl acrylate in DMSO and IPA at ambient temperature using Cu(0) wire is investigated. Tetra- and octafunctional initiators were utilized to facilitate the synthesis of well-defined PDMAEA star homo and block copolymers with a range of molecular weights (M-n similar to 5000-41 000 g mol(-1)). Both solvents demonstrated to be excellent media for the controlled polymerization of DMAEA, yielding narrow molecular weight distributions (D similar to 1.1) when the reactions were ceased at similar to 40% conversion. Interestingly, at high conversions (typically >55%) high and low molecular weight shoulders were evident by SEC when DMSO and IPA were used, respectively, suggesting a large extent of termination and/or side reactions at prolonged reaction times. Nevertheless, high end group fidelity could be maintained when immediate precipitation of the polymers (at lower conversion) was performed, yielding low dispersed P(DMAEA-b-MA) star block copolymers (D < 1.19, M-n similar to 20 000 g mol(-1)). Importantly, guidelines on how to prevent hydrolysis, termination, and side reactions of PDMAEA as well as how to purify and store such materials are also provided and discussed.