A novel TiO2/β-cyclodextrin (TiO2/β-CD) organic-inorganic hybrid nano-material with alveolate structure is fabricated using a facile one-step strategy. The alveolate TiO2/β-CD hybrid nano-material exhibits outstanding photocatalytic activity and recyclability on photocatalytic water splitting. The production of H2 evolution of TiO2/β-CD hybrid reaches to 5800 μmolg-1 after 8 h without noble metal. Meanwhile, the recyclability of the TiO2/β-CD photocatalyst is found to be no obvious decrease with the H2 generation after third successive runs. The formation of the oxygen defects occurred on coordinatively unsaturated Ti-sites by the introduction of β-CD at the outer surface of TiO2 could be the predominant active species in the photocatalytic system. Due to the alveolate heterogeneous structure of TiO2/β-CD hybrid play a role as “channel” for photocatalytic activity. The channel can capture more electrons and light, provides a larger area for reaction. This work provides a promising approach to construct noble metal-free and more stabilized organic-inorganic nanocomposite photocatalysts applied in the photocatalytic water splitting.