Ceria-titania doped highly ordered hexagonal and cubic mesoporous silica composite samples with varying amounts of Ce and Ti have been synthesized using hexadecyltrimethylammonium bromide (CTAB) surfactant as a template under basic conditions in the presence of ammonia. The removal of the template resulted in the formation of mesoporous composites doped with Ce and Ti, which were thoroughly characterized via small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXRD), N2 adsorption, scanning and transmission electron microscopy analysis with energy-dispersive spectrometry mapping (SEM-TEM-EDS), inductively coupled plasma atomic emission spectrophotometry (ICP-AES), and ultraviolet-visible diffuse reflectance spectrometry (UV-visible). The electronic states of Ti and Ce species present on the surface of silica were also investigated by X-ray photoelectron spectroscopy (XPS). The catalytic activity of these Ti-modified ceria-silica samples for the photodecomposition of rhodamine B under visible-light irradiation was investigated. The results revealed that a sample with a higher Ti content, as well as equal amounts of Ce and Ti, displayed higher catalytic activity for the photodegradation of the organic dye rhodamine B.