We studied the effects of H2O2 oxidation without metal catalysts and under neutral conditions on morphologies and structures of the multiwalled carbon nanotubes (MWNTs). The formation of surface functional groups and changes in nanotube structures, morphology, and thermal stability during oxidation were analysized by X-ray photoelectron spectroscopy, X-ray diffraction, Raman spectra, high-resolution transmission electron microscopy, and thermogravimetric analysis. Several functional groups such as carboxylic (-COOH), carbonyl (-C=O), and hydroxyl (-OH) groups were formed on the surface of MWNTs; however, hydroxyl groups were preferentially formed and reached a maximum atomic concentration of about 46% in 4 days of oxidation. The graphitization degree decreased in the first day of oxidation; however, it readily increased in the continued oxidation days.