Photocatalytic hydrogen production with gas-phase reactions in high vacuum was examined for nanocrystalline anatase-type titanium dioxide (TiO2) thin films. The hydrogen generation process on platinized TiO2 specimens was investigated using a quadrupole mass spectrometer at a real-time scale under various partial pressures of gaseous methanol and water. As a result, hydrogen generation was successfully detected under ultraviolet ray (UV) illumination even in high vacuum (∼ 10−7 Torr). And the amount of produced H2 largely depends on the temperature of TiO2 samples, probably due to different surface states of TiO2. This study suggests the possibility of new high-speed H2 production system with gas-phase photocatalytic reactions.