Since the radical polymerization of electron-deficient monomers redox-initiated by pairs of tertiary amine-transition metal cation complexes in the high oxidation state, as a mono-centered radical initiation mechanism, offer 100% alpha-amino telechelic polymer, the analogous processes by pairs of poly(tertiary amine)-transition metal cation complexes in the high oxidation state were designed with an objective to directly yield graft copolymers. Conventional radical polymerization of 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) was performed to yield PDMAEMA as the high-molecular weight (MW) poly(tertiary amine), and the radical polymerization of N,N-dimethylacrylamide (DMAAm) redox-initiated by FeCl3-PDMAEMA pairs in aqueous solutions was conducted then. The kinetics of polymerization was monitored by gas chromatography, and the polymerizing resultants were characterized by gel-permeation chromatography and nuclear-magnetic resonance spectroscopy. On the one hand, the radical polymerization of DMAAm with PDMAEMA as the reducing agent evolved at a faster rate than those with low-MW analogues as the reducing agent. On the other hand, the MW of the polymerizing resultants increased by several folds initially, maintained almost constant during the middle stage, and adversely decreased notably. The results suggested that FeCl3-PDMAEMA redox-initiated radical polymerization occurred predominantly during the early stage, leading to PDMAEMA-g-PDMAAm. However, the formation of free PDMAAm chains, rather than grafted side chains, became increasingly significant with the polymerization. Control experiments confirmed that serious hydrolysis occurred with PDMAEMA in the presence of Fe-II complexes, leading to free low-MW tertiary amines, which would form redox initiator pairs with Fe-III complexes to initiate radical polymerization of DMAAm, leading to free PDMAAm chains. Water-soluble hydrolysis-resistant polymeric multi-functional poly(tertiary amine)s would help to produce graft copolymers at a favorable rate.