The surface of aerosilogel and macroporous and microporous glasses was modified with aromatic sulfo groups (≡Si(CH₂) ₂-C₆H₄-SO₃H) by the chemical assembly method. Composite solid electrolytes containing Nafion were prepared from the silica matrices with a chemically modified surface. The proton conductivity of the materials was studied by impedance spectroscopy. Composite materials based on Nafion and aerosilogel matrices and macroporous glasses with grafted ≡Si(CH₂)₂-C₆H₄-SO ₃H groups showed the highest proton conductivity.