Mesoporous SBA-15 molecular sieves, with large surface area and homogeneous pore diameters, are commonly used as catalysts and adsorbents. In this work, SBA-15 was functionalized with 3-(methacryloyloxy)propyltrimethoxysilane (MPTMS) and then polymerized sol–gel onto the channel walls. The new materials were characterized by solid-state NMR, Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD), nitrogen adsorption–desorption measurements, thermogravimetric analysis (TGA) and elemental analysis. The adsorption properties of SBA-15, MPTMS modified SBA-15 and polymerized sol–gel SBA-15 to Rhodamine B (RB) were studied comparably. The modified SBA-15 materials have effective adsorption characters to RB. These results demonstrate that these new materials have potential applications in the treatment of RB pollution from environment.