In the present study, pure TiO2 and hybrid TiO2/CNTs nanomaterials are prepared by sol gel technique. Post heat treatment is performed at 600, 800, and 1000 degrees C, respectively. The structural characterizations are performed by field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction and synchrotron X-ray absorption spectroscopy techniques. Experimental results show that anatase to rutile transformation can be observed for pure TiO2 nanomaterials after heat treatment at 800 degrees C. The anatase to rutile transformation is inhibited by carbon nanotubes, and therefore only anatase phases for TiO2 nanomaterials can be observed in the hybrid nanomaterials. The 600 degrees C hybrid nanomaterials show a microstructure with CNTs covered by continuous TiO2 films of numerous small nanoparticles. After applying heat treatment on the hybrid nanomaterials at 1000 degrees C, only TiO2 nanoparticles adhere individually to the uncovered CNTs. Though all hybrid nanomaterials exhibit anatase TiO2, synchrotron X-ray absorption spectra investigations reveal that hybrid TiO2/CNTs exhibit different electronic properties as compared to those of pure TiO2 nanomaterials.