Rheological characterization of the as-prepared gels leads to the same qualitative trends as reported for other hetero-complementary coupled networks of star polymers. Modulus data on a quantitative basis are clearly below the expectations and in the range of recent experiments on comparable co-polymer gels. The equilibrium swelling degrees show a power law dependence on the polymer volume fraction at preparation, 𝜙 0 -0.40±0.01 . This dependence is in between the scaling limits of entanglement-free networks and entanglement dominated systems and is only coincidentally close to the classical prediction. An essential aspect of the work was to find out which influence the reaction conditions have on the network microstructure. For this purpose, MQ NMR investigations were carried out which provided information on occurring connectivities (see Scheme 1) and possible network defects.