Highly ordered TiO2 nanotube film on a titanium foil was prepared by an anodization process. Then, the anatase-rutile hybrid crystal TiO2 materials fabricated at 700 degrees C were used as an anode for electrochemical synthesis of benzoic acid from toluene. At this anode, the highest yield of benzoic acid at ambient temperature is 27.5%, but it rises to 32.8% at 90 degrees C with a toluene conversion rate of 49.1%. The yield is increased mainly due to the hybrid crystal of the novel anode, and the formation of carbonized TiO2 nanotube surface at the Ti substrate together facilitates the charge transfer and induces a significant enhancement in the anode reactivity. Moreover, the effects of calcination temperature on the morphology, structures and crystallization of the TiO2 nanotubes were discussed in detail. A synergistic effect of electric field, visible light irradiation, and temperature for benzoic acid synthesis at the anatase-rutile hybrid crystal TiO2 was discussed. To our knowledge, this is the first study about the use of the carbonized anatase-rutile hybrid TiO2 nanotube films electrode in benzoic acid synthesis under the coupling fields. This study provides new insights into high-performance metal oxide electrode materials for organic synthesis.