Vertically oriented nanotubular TiO2 arrays were formed by a simple anodization process. Hydrogen storage studies were carried out on the TiO2 nanotubular arrays having different diameters by charging and discharging hydrogen with potentiostatic/galvanostatic control. The hydrogen storage capacities of the nanotubes were only marginally affected by the tube diameter. Concentration of oxygen vacancies as defects influenced the hydrogen storage of the nanotubes. Annealing of the TiO2 nanotubes in argon atmosphere increased the defect density and decreased the hydrogen discharge during initial charge–discharge cycles. Hydrogen storage studies through electrochemical route did not show significant storage capacity of TiO2 nanotubes. Diffusion of hydrogen as protons and interference of the double layer capacitance of nanotubes could be attributed to the lower hydrogen storage capacity.