Adaptive and amphiphilic poly(N,N-dimethylamino-2-ethyl methacrylate-graft-poly[ε-caprolactone]) conetworks (netP(DMAEMA-g-PCL)) were synthesized from a combination of controlled polymerization techniques. Firstly, PCL cross-linkers were produced by ring-opening polymerization (ROP) of ε-CL initiated by 1,4-butane-diol and catalyzed by tin(II) 2-ethylhexanoate ([Sn(Oct)2]), followed by the quantitative esterification reaction of terminal hydroxyl end-groups with methacrylic anhydride. Then, PCL cross-linkers were copolymerized to DMAEMA monomers by atom-transfer radical polymerization (ATRP) in THF at 60°C using CuBr complexed by 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) and 2-ethyl isobutyrylbromide (EiBBr) as catalytic complex and initiator, respectively. A comprehensive study of gel formation was carried out by employing dynamic light scattering (DLS) to determine the gel point as a function of several parameters and to characterize the viscous solutions obtained before the gel point was reached. The evolution of the mean diameters was compared to a model previously developed by Fukuda and these attest to the living formation of the polymer co-network. Furthermore, we also demonstrated the reliability of ATRP for producing well-defined and homogeneous polymer conetworks by the smaller deviation from Flory's theory in terms of cross-linking density. For sake of clarity, the impact of polymerization techniques over the final structure and, therefore, properties was highlighted by comparing two samples of similar composition, but that were produced by either ATRP or thermal-initiated free-radical polymerization (FRP).