The hybrid mesoporous materials, PW11/SBA-15, were synthesized using tetraethoxysilane (TEOS) and lacunary polyoxometalate Na7PW11O39 (PW11) by a co-condensation approach in the presence of triblock copolymer EO20PO70EO20 (P123) as a template. The resultant materials were characterized by infrared (IR) spectroscopy, UV-Vis diffuse reflectance spectroscopy (UV-Vis/DRS), powder X-ray diffraction (XRD), N2 adsorption-desorption, and transmission electronmicroscopy (TEM). Results show that the Keggin units are retained perfectly and grafted onto the pore walls of the mesoporous silica by covalent linkage, and an ordered hexa nal packing of channels with homogeneous pore diameters is obtained in the materials. The prehydrolysis time of TEOS influences the construction of the ordered mesostructure significantly. The long-range ordered mesophase increases as the prehydrolysis time increases because of the salt-out effect of PW11, which is associated with solubility of the polyoxometalate precursors.