Three new amine-based tripodal copper complexes-tris(2-(diethylamino)ethyl)amine/CuBr (Et6TREN/CuBr), 2,4-dimethyl-6-bis(2-(dimethylamino)ethyl)aminomethylphenoxy (N-tetramethyltriaminephenoxy) (Me(4)TAPH/Cu-II), and N,N-bis[(2-pyridyl)methyl]-2-aminomethylpyrrolide (BPPY/Cu-1)were prepared and investigated as ATRP catalysts in order to understand the effect of steric hindrance and the presence of a charged anionic group on the performance of catalysts based on branched tetradentate amine ligands in ATRP. Catalysts based on these ligands were evaluated for n-butyl acrylate (BA) polymerization, and their performance was compared with those of known analogues: Me6TREN and N-tetraethyltriaminephenoxy (Et(4)TAPH) copper complexes. When compared to Me6TREN/CuBr-mediated polymerization, the more sterically hindered Et6TREN/CuBr catalyst complex promoted a much slower and less controlled BA polymerization. This indicates that bulkiness around the metal center had a strong effect on the ATRP equilibrium. The Me(4)TAPH copper(II) complex was also synthesized and used as an ATRP catalyst in a simultaneous reverse and normal initiation system. The rate of propagation was slightly lower, and control over the polymerization was poorer, than in a Me6TREN-mediated polymerization. However, its catalytic performance was much better than the N-tetraethyl analogue, Et(4)TAPH, copper complex. The much less hindered BPPY copper(l) complex promoted faster BA polymerization in DMF than Me6TREN/CuBr-mediated polymerization, but the control over the polymerization was poor. These results indicate that steric hindrance is an important factor for developing new catalyst complexes for both high activity and control over ATRP. Selected complexes with charged ligands demonstrated enhanced ATRP activity.