Tungsten-substituted mesoporous MCM-48 materials are successfully synthesized at 393 K by a one-step co-condensation sol–gel method. The prepared samples with different Si/W ratios are characterized by X-ray diffraction (XRD), nitrogen adsorption, high-resolution transmission electron microscopy (HRTEM), diffuse reflectance UV–visible spectroscopy and FT-IR, and the results indicate the presence and good dispersion of tungsten species inside the silica pores, the Si/W ratio is controlled above 28. When the Si/W ratio is less than 28, though no bulk tungsten is detected outside the MCM-48 mesoporous silica, the pore structure order becomes worse.