Photocatalytic properties for hydrogen production were investigated on layered titanium compounds intercalating CdS in the interlayer, which were prepared by direct cation exchange reactions and sulfurization processes. The photocatalytic activity of the compounds intercalating CdS was superior to those of simple CdS and the physical mixture of CdS and metal oxides. The improvement might be attributed to the formation of microheterjunctions between the CdS nanoparticles and the layers of oxides. The activity was also enhanced by the substitution of Nb for partial Ti in K2Ti4O9, which led to the increase in CdS content in the interlayer and the rapid transport of photogenerated electrons through the layer of metal oxide.