In this paper, three types of CNT/$TiO_2$ composite electrodes were prepared with different methods. The changes in XRD patterns showed that the Electrode A contained a mixed phase of anatase and rutile while the Electrode B and Electrode C contained a typical single and clear anatase crystal structure. From SEM micrographs, $TiO_2$ particles were adhered on the surface of the CNT network in the forms of small clusters. The results of chemical elemental analysis indicated that the main elements such as C, O and Ti were existed. The results demonstrated that the efficiency of photoelectrocatalytic (PEC) oxidation for methylene blue (MB) was higher than that of photocatalytic (PC) oxidation. There was a clear enhancement trend of the MB degradation using the prepared CNT/$TiO_2$ composite electrodes with an increase of applied potential. Finally, the prominent PEC activities of the CNT/$TiO_2$ composites could be attributed to combination effects of photo-degradation of $TiO_2$, electron assistant of CNT and function of applied potential.