ATRP of 2-(N,N'-dimethylamino)ethyl acrylate (DMAEA) was investigated using CuBr or CuCl with different multidentate ligands. the catalyst was found active for DMAEA polymerization when ligated with tris[2-N,N'-dimethylamino)ethyl]amine. Good control over molecular weight was achieved, but quaternization of the terminal monomeric/polymeric tertiary amine by the C-Br group of polyDMAE caused chain termination. Using a chloride-based system helped to suppress chain termination. Amphiphilic poly(methyl acrylate)-block-polyDMAEA was synthesized uing polyMA as a macroinitiator.