Nickel species were loaded on titanate nanotubes (TNT) as a hydrogen evolution cocatalyst by an impregnation-calcination method. Nickel chloride, nickel nitrate and nickel acetate were used as the precursors. More Ni2+ ions intercalate into the interlayer of TNT when nickel chloride is used as the precursor. In the calcination process, the titanate transforms into anatase TiO2, and Ni2+ ions are reduced and doped partly in TiO2 and titanate. The Ni2+ ions intercalated into TNT inner can promote the phase transformation, growth of metal Ni particles and the Ni2+ doping. The formed Ni particles can be oxidized in air to form core/shell Ni@NiO structure. The Ni2+ doping promotes the formation of oxygen defects and increases the conductivity of TNT. The photocatalytic activity of Eosin Y-sensitized nickel-modified TNT for hydrogen evolution was investigated. The TNT modified with nickel chloride exhibit higher activity, which can be attributed to the higher conductivity and more effective formation of Ni@NiO structure. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.