In this paper, a new and efficient way to oxidize and functionalize the multi-walled carbon nanotubes (MWNTs) has been developed by using a combination of ultraviolet (UV) irradiation and Fenton oxidation process, namely UV/Fenton oxidation treatment. Comparing with conventionally individual Fenton oxidation treatment of MWNTs, UV/Fenton combined treatment improved the etching rates and efficiencies and hence reduced the time for surface modification of MWNTs, which was proved to be an effective method in etching and functionalizing CNTs. The formation of new functional groups, structural changes and thermal stability during oxidation period were characterized by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and could be clarified by thermogravimetric analysis (TGA), which showed that it was under UV irradiation conditions that MWNTs could be rapidly functionalized with hydroxyl, carbonyl and carboxyl groups in the presence of Fenton reagents, originating from the increase in the gross HO·concentration and the existent synergetic effect when using UV irradiation combing with Fenton oxidation process. Introduction of such new oxygen-containing functional groups was attributed to attacks of HO·on defect sites and unsaturated bonds of C=C in the MWNTs sample, which should play an important role in accounting for the FTIR and Raman spectral changes.