We report here on the extension to elastomers of the idea of inducing nanoscale ordering in supramolecular ploymer systems based on the principle of hydrogen bonding between amphiphiles and (block co-)polymers. Three different networks have been synthesized using 4-vinylpyridine and divinylbenzene (0.5, 1.0, and 2.0 mol %, respectively) and are further complexed with pentadecylphenol or nonadecylphenol. For low degrees of cross-linking (0.5 and 1.0 mol % divinylbenzene), mesomorphic structures are formed, and order-disorder transitions are observed by small-angle X-ray scattering (SAXS) and differential scanning calorimetry. For the highest degree of cross-linking (2.0 mol % divinylbenzene), mesomorphic structures is no longer observed. The presence of ordered lamellar structures is confirmed by transmission electron microscopy (TEM). SAXS and TEM clearly reveal the deteriorating effect of an increasing degree of cross-linking on the structure formation.