The hydrogen storage property of the porous/hollow TiO2 using yeast as template was investigated. It is demonstrated that crystalline TiO2 forms until the temperature reaches 620 °C. The product is composed of TiO2 and minor amount of H2Ti3O7 after heat treatment. The porous/hollow TiO2 with a specific surface area of 252.6 m2/g is obtained due to the removal of yeast. Pressure-composition isothermal (P-C-I) curve of TiO2 shows that a reversible hydriding/dehydridng process occurs at 30 °C, suggesting an obvious physisorption. The change of the chemical bond in Fourier-transform infrared (FT-IR) spectrum in hydriding/dehydridng indicates that hydrogen reacts with OH group on TiO2 surface even at 30 °C. The porous/hollow TiO2 collapses as cycles increase and the corresponding specific surface area decreases dramatically. Contrary, the hydrogen uptake increases with increasing of temperature, which is caused by chemisorption.