Anodization of Ti in acidified fluoride solution results in an ordered nanotubular titanium oxide surface. In this study, vertically oriented arrays of TiO 2 nanotubes were prepared by incorporating nitrate and phosphate species during the anodization process. These nanotubes were annealed at 650 °C in a carbonaceous atmosphere using a chemical vapor deposition (CVD) furnace for a brief period. The carbon-modified nanotubular TiO 2 produced a photo-current density of more than 2.75 mA cm −2 at 0.2 V Ag/AgCl under solar light illumination. This photo-current density corresponds to a hydrogen evolution rate of about 11 l h −1 using a photo-anode of 1 m 2 area. The enhanced hydrogen evolution behavior of carbon-modified nanotubular TiO 2 is highly reproducible and sustainable for long duration. Annealed (at 350 °C in nitrogen atmosphere) TiO 2 nanotubes showed improved photo-activity as compared to the as-anodized or thermally oxidized TiO 2 photo-anodes.