The combination of polymers with macromers derived from inorganic species and oligomers to yield controlled hyperstructures can potentially allow the design of materials with tunable mechanical, optoelectronic properties and chemical behavior. In this work, novel hybrid structures were processed based upon the controlled insertion of macromers derived from inorganic groups and oligomers into previously chemically modified polymer frameworks. The chemical procedure involved a series of steps that started with the creation of a functionalized framework to act as host for the construction of the polymer macromer hyperstructures. The designed polymer framework was obtained by incorporating highly polar groups, such as sulfonic acid, into poly(aryl ether sulfones). Following this step, the newly promoted reactive sites were used to insert alkoxysilane groups through reacting modified poly(aryl ether sulfones) with specifically selected silane compounds. The chemical reactions and the obtained novel structures were characterized using NMR, FTIR, AFM and thermal analysis. Results showed that structural parameters such as the concentration of siloxane bonds across the material and the density of cross-links could be controlled by selecting different conditions of reaction. Completely homogeneous and also heterogeneous, but still controlled, structures could be produced using the described procedure. The developed polymer structures containing controlled profiles of concentration, densities and chemical functionalities can have tailorable mechanical properties and chemical activity.