This study investigates the microstructures of multi-walled carbon nanotubes (MWNTs)/TiO(2) nanocomposites, obtained by sol-gel and hydrothermal processes. The synthesized nanocomposite materials were characterized by x-ray diffractometry (XRD), Brunauer-Emmett-Teller (BET) adsorption analysis, transmittance electron microscopy (TEM), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy, and x-ray photoelectron spectroscopy (XPS). The effects of the synthetic procedures and MWNTs on the morphology and photocatalytic activity of the nanocomposites were studied. The photocatalytic activity of the MWNTs/TiO(2) nanocomposite was elucidated based on the photooxidation of NO(x) under UV light illumination. A fleck-like and well dispersed TiO(2) microstructure on the surface of the MWNTs was observed in the sol-gel system, while compact and large aggregated particles were found in the hydrothermal procedure. The nanocomposite prepared by the sol-gel system exhibits better photocatalytic activity for NO oxidation (from 20.52 to 32.14%) than that prepared by the hydrothermal method (from 22.58 to 26.51%) with the same MWNT loading (from 0 to 8 wt%), respectively. The optimal MWNT content in the nanocomposite was considered at 8 wt%. Additionally, results confirm that the introduction of MWNTs will cause the NO(2) to be more consumed than NO in the photocatalytic experiments, leading to more complete NO(x) photooxidation. These observations indicate that the different TiO(2) distributions on the MWNT surfaces and MWNT contents in the materials would determine the morphology, the physicochemical and photocatalytic characteristics for the nanocomposite materials.