Layered Double Hydroxide (LDH)/TiO2 nanocomposites with photocatalytic properties were synthesized by both impregnation and the direct coprecipitation of LDH matrices using a colloidal suspension of TiO2 nanoparticles. While the two methods led to an efficient TiO2 nanoparticle immobilization, the direct coprecipitation allowed us to tune the amount of immobilized TiO2 within the materials. The LDH/TiO2 nanocomposites obtained were deeply characterized by chemical analysis (ICP-AES), Powder X-ray diffraction (XRD), Fourier Transformed Infra-Red (FTIR), Thermogravimetric analysis (TGA), and High-Resolution Transmission Electron Microscopy (HRTEM). Clearly, the immobilization of TiO2 by direct coprecipitation promoted a modification of the textural properties and a net increase in the surface area. The crystallized TiO2 nanoparticles can be distinctly visualized by HRTEM at the surface of the layered material. Several parameters, such as the nature of the chemical composition of LDH (ZnAl and MgAl), the method of immobilization and the amount of TiO2, were shown to play a crucial role in the physicochemical and photocatalytic properties of the nanocomposites. The photocatalytic efficiency of the different LDH/TiO2 nanocomposites was investigated using the photodegradation of a model pollutant, the Orange II (OII), and was compared to a pure TiO2 colloidal solution. The degradation tests revealed that the nanocomposite obtained from MgAl LDH at a low MgAl LDH/TiO2 ratio was the most efficient for the photodegradation of OII leading to complete mineralization in 48 h.