A novel tetradentate amine ligand namely N,N,N′,N″,N‴;,N‴;‐hexaoligo(ethylene glycol) triethylenetetramine (HOEGTETA) was employed in the homogenous ATRP of MMA in anisole using CuBr and CuBr2 as the catalyst and ethyl 2‐bromoisobutyrate (EBiB) as an initiator. The effect of the polymerization temperature and the various ratios of Cu(I) to Cu(II) were investigated in detail. Moreover, we demonstrated the ATRP of MMA by using only Cu(II) in the absence of any free radical initiator, reducing agent, or air. The ATRP of MMA with the use of only Cu(II) and HOEGTETA or N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) resulted in well‐defined PMMA.
