Novel macroporous functionalized copolymers with different cross-linker concentrations and porosity parameters were synthesized by reaction of the pendant epoxy groups of poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) (poly(GMA-co-EGDMA)) with hexamethylene diamine 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and alpha,omega-diaminopropyl poly(dimethylsiloxane). The copolymers were prepared in forms, of spherical beads and characterized by Fourier transform infrared (FTIR); C-13 and Si-29 solid-state NMR, mercury porosimetry, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Copolymers prepared with the higher cross-linker concentrations have better thermal stability, higher glass transition temperatures; higher specific surface areas, and smaller pore diameters that correspond to half Of the pore volumes. Out results show that functionalization significantly changed porosity parameters, mechanism of thermal degradation; and increased thermal, stability in comparison with the initial copolymers. These macroporous copolymers could potentially have many applications, i.e. for sorption of heavy and precious metals or as Material for gas chromatography columns.