A novel heterogeneous photocatalysts HCa2TaxNb3-xO10/(ZnS, PbS) (x = 0, 1) were fabricated by intercalation and exchange reactions. The physicochemical properties of the photocatalysts were analyzed by Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Ultraviolet-visible spectroscopy (UV-Vis), Fourier transformed infrared spectra (FT-IR) and Photoluminescence technique (PL). The photocatalytic activity of the HCa2TaxNb3-xO10/(ZnS, PbS) was evaluated by photocatalytic H-2 production in an aqueous solution containing SO32- and S2- as a sacrificial agent under UV light irradiation. HCa2TaxNb3-xO10/(ZnS, PbS) possessed a higher gallery height than that of HCa2TaxNb3-xO10, which indicated the formation of an intercalated nanomaterial and a heterogeneous catalyst. The results showed that these samples presented strong photocatalytic activity even without co-catalyst noble metal Pt. The photocatalytic activity of HCa2TaxNb3-xO10/(ZnS, PbS) was several times higher than that of unsupported HCa2TaxNb3-xO10. The heterogeneous electron transfer from guest ZnS, PbS to host HCa2TaxNb3-xO10 layer and the substitution of Ta for partial Nb seemed to play an important role to enhance the photocatalytic activity. (C) 2013 Elsevier B.V. All rights reserved.