Preparation of model amphiphilic polymer networks (APNs) using various polymerization mechanisms and/or organic coupling reactions are reviewed. A particular emphasis is made on controlled/“living” polymerizationtechniques in their diversities and how they impact on the structure-reactivity relationships. Advantages and limitations of each technique, as well as improvement of final physical/dynamical properties, are thoroughly discussed and compared for some of the mechanisms. Confrontation of experimental data with Flory’s theory is also displayed in the particular case of controlled radical polymerization (CRPs) techniques. Synthesis of model APNs by the end-linking process using efficient organic coupling reactions such as Michael-type addition, Huisgen 1,3-dipolar cycloaddition and thiol-ene click reactions are deeply illustrated and discussed.