Amphiphilic networks segregated in hydrophilic and hydrophobic domains are very attractive materials because they show unique properties related to the combination of both components. In this work, these types of networks have been obtained in a very simple way by a single standard bulk radical photocopolymerization of vinylpyrrolidone, and n-butyl methacrylate, in the presence of 1 mol % of cross-linkers with different methacrylate or VP-like functionalities. The cross-linker fiinctionalities have been shown to have a strong influence on the sol content and on the different properties of the materials, such as segregation or the variation of the storage modulus with temperature and hydration. The compositional data of the polymeric chains of this sol content are in good agreement with the theoretical prediction of the polymerization carried out assuming that the reaction may be described compositionally by the terminal model. The most efficient cross-linking was obtained using an asymmetric cross-linker bearing simultaneously methacrylate and VP-like groups.