Abstract TiO 2–carbon nanotube (CNT) heterojunction arrays on Ti substrate were fabricated by a two-step thermal chemical vapor deposition (CVD) method. CNT arrays were first grown on Ti substrate vertically, and then a TiO 2 layer, whose thickness could be controlled by varying the deposition time, was deposited on CNTs. Measured by electrochemical impedance spectroscopy (EIS), the thickness of the TiO 2 layer could affect the photoresponse ability significantly. About 100 nm thickness of the TiO 2 layer proved to be best for efficient charge separation among the tested samples. The optimized TiO 2–CNT heterojunction arrays displayed apparently higher photoresponse capability than that of TiO 2 nanotube arrays which was confirmed by surface photovoltage (SPV) technique based on Kelvin probe and EIS. In the photocatalytic experiments, the kinetic constants of phenol degradation with TiO 2–CNT heterojunctions and TiO 2 nanotubes were 0.75 h −1 ( R 2 = 0.983) and 0.39 h −1 ( R 2 = 0.995), respectively. At the same time, 53.7% of total organic carbon (TOC) was removed with TiO 2–CNT heterojunctions, while the removal of TOC was only 16.7% with TiO 2 nanotubes. These results demonstrate the super capability of the TiO 2–CNT heterojunction arrays in photocatalysis with comparison to TiO 2-only nanomaterial.