N2O4 was easily impregnated on silica gel to give a stable heterogeneous reagent N2O4/SiO2 (I). Chemoselective deprotection of trimethylsilyl ethers to the corresponding alcohols was achieved in the presence of I in CH2Cl2 in excellent yields. The stability, easy preparation and high selectivity of the reagent make this method as a useful procedure for the selective deprotection of TMS ethers at room temperature.