Since tertiary amines (C

α

-H) can be oxidized by peroxides and transition metal cations in high oxidation states into C

α

· radicals to initiate vinylic polymerizations of methacrylates

Cu

2+

and 2-(

N

N

-dimethylamino)ethyl methacrylate (DMAEMA) form a polymerizable redox initiating pair

in which DMAEMA serves as an intrinsically reducing inimer. CuSO

4

-catalyzed aqueous self-initiated radical polymerizations of DMAEMA were successfully performed at ambient temperature

via

a continuous Cu

2+

-tertiary amine redox initiation based on catalyst regeneration in the presence of O

2

. The polymerization kinetics was monitored by gas chromatography and the structure of PDMAEMA was characterized by gelpermeation chromatography

nuclear magnetic resonance spectroscopy

laser light scattering and online intrinsic-viscosity analysis. Both the monomer conversion and the molecular weight of PDMAEMA increase with the reaction while the molecular weight distribution maintains rather broad

as the Cu

2+

-DMAEMA redox-initiation leads to linear PDMAEMA chains with terminal methacryloxyl moieties

and the Cu

2+

-PDMAEMA redox-initiation results in branched chains. The branched topology forms and develops only for the high-MW components of the PDMAEMA. Our results provide a facile strategy to prepare branched polymers from such commercially available intrinsically reducing inimers using a negligible concentration of regenerative air-stable catalysts.