A series of mesoporous silicalites was synthesized using different compositions of tetraethylorthosilicate and methyltriethoxysilane (MTES) as the silica source. Cetyltrimethylammonium bromide was used as the organic template. Their detailed pore structures were investigated by transmission electron microscopy, X-ray diffraction, and N2 adsorption method. The thermal properties of these silicalites were studied by thermogravimetric analysis. The increased amount of MTES destroyed mesoporous channels and reduced pore sizes from 3.4 nm to 2.8 nm in calcined silicalites. The calcined silicalite transformed completely into an amorphous state at 30% MTES loading. Methyl pending groups of MTES hindered the structural ordering of ≡Si-O- frameworks, resulting in an amorphous structure. This was caused by the insufficient formation of supramolecular assembly with the organic template. No capillary condensation step was found in MS 7/3 silicalite. The other capillary condensation steps shifted toward the lower relative pressure with increasing MTES content, indicating the reduction of pore sizes.