ZnO:SiO2 films are intensively investigated for optical and electronic applications. Additionally, porous SiO2 films are of great interest as catalyst and gas-sensing materials. The sol-gel method is an low-cost process for the deposition of meso- and microporous silica-based films. The present paper the effect of the withdrawal speed on the microstructure and optical properties of mesoporous films obtained by the sol-gel method. The morphology of the films was investigated by atomic microscopy and the overall structure was studied by X-ray diffraction. The structure and size of oxide nanoparticles embedded in the silica matrix were investigated in more detail by transmission microscopy. These techniques showed ZnO:SiO2 films with crack-free mesoporous morphology and efficient embedding of ZnO nanoparticles with (100) preferred orientation. Furthermore, the transmittance (in the visible and near infrared regions) and the optical band gap value were observed with withdrawal speed. It is shown that ZnO:SiO2 nanocomposites films which possess ZnO exhibiting a (100) orientation, with possible special applications in non-linear optics, could be the low-temperature crystallization sol-gel method.