A new approach for the synthesis of model amphiphilic polymer co-networks (ACNs) based on a heterocomplementary coupling reaction of a 2-(4-nitrophenyl)-benzoxazinone terminated tetra-arm polycaprolactone star (tetra-PCL) with an amino-terminated tetra-arm polyethylene glycol star (tetra PEG) is presented. The reaction conditions (solvent, concentration, and temperature) were varied widely. Reaction kinetics and gelation were analyzed with high-resolution NMR spectroscopy and computer simulations. The results agree with a nearly homogeneous mixture where local composition fluctuations affect kinetics only after most of the molecules are attached to the gel. Viscometry, dynamic light scattering data, and literature data for the solubility parameters were combined to provide estimates for the Flory-Huggins interaction parameter of the two star polymers in toluene, chloroform, and THF as solvents. These estimates allow one to collapse equilibrium swelling data in different solvents on a universal curve. Multiple quantum NMR analysis shows an enhanced formation of double connections between the same pair of stars as compared to preceding work on tetra-PEG gels made by the same cross-linking strategy but with a different coupling reaction. Besides this last observation, the remaining results indicate that the networks possess a near model-like structure with only a small fraction of pending arms as the most relevant type of network defects.