The synthesis and characterization of polysiloxane crown ethers 5,8,11, are reported in this work. Tetraethyl orthosilicate (TEOS), tetraethylene glycol and sodium metallic were employed as precursors and the polysiloxanes obtained were characterized by elemental analysis, infrared (FTIR) spectra, thermogravimetric analysis (TG), differential scanning calorimetry (DSC) and nuclear magnetic resonance of 1 H, 13 C and 29 Si. The hybrid surfaces were analyzed using scanning electronic microscopy (SEM). All hybrids showed a synergistic effect from a thermodynamic viewpoint, since the crown ether analogue (15−crown−5) has a low decomposition temperature. The proportional increase of the silica precursor (TEOS) improved the thermal and mechanical properties.