The influence of hydrogen on the formation of porous TiO2 in alkaline solution was investigated using an electrochemical measurement, a scanning electron microscope, and a grazing incident X-ray diffraction technique. The porous TiO2 was not obtained on the surface of titanium in 5 M NaOH solution at 303 K for 3 h. When the titanium was charged with hydrogen in 1 M H2SO4 at 303 K for 1 h before immersion, the porous TiO2 was readily produced on the surface under the same experimental conditions. The anodic polarization measurement indicated that the hydrogen-charged titanium was more readily dissolved in alkaline solution than the titanium. The cathodic reaction was the hydrogen evolution reaction on both the titanium and the hydrogen-charged titanium. For titanium, although the hydrogen penetrated into the inside of the material due to the side reaction of hydrogen evolution, the hydrogen content in the inside was so small that porous TiO2 was not produced under this condition.