In analogy to the tetra-PEG gels, a key aspect in the synthesis of model ACNs is the heterocomplementary linkage of structurally defined hydrophilic and hydrophobic star polymers via their end groups. Typically, fast click reactions, such as azide-alkyne cycloaddition, condensation reactions of amino groups with activated ester bonds, as well as the addition reaction of benzaldehyde and benzaacylhydrazide terminal groups have been used for the synthesis of A2B4and A4B4-type ACNs. These reactions provide high conversions within a short time. While this may initially appear to be an advantage, it entails the risk that the components forming the network do not mix properly. As a result, additional defects and large-scale heterogeneities inducing shielding of reactive groups may occur. Another influencing factor is a possible segregation of the chemically different building blocks during the ACN formation, which is also assumed to have an effect on network inhomogeneities. These aspects have hardly been considered in previous work.