To fulfill photocatalytic hydrogen production, Ag-doped ZnS photo catalyst was prepared by template hydrothermal method and solution infiltration and reduction method. The structure and optical property were studied by XRD, SEM and UV-vis, respectively. The photocatalytic activity of the catalysts was evaluated by splitting Na₂S+Na₂SO₃ solution into H₂. The results show that in acid bath with a small amount of template and a large amount of Thiourea and Zn(Ac)₂, the sample is of rod structure and exists mainly in the form of sphalerite; whereas the sample is of ball structure and co-exists in the form of wurtzite and sphalerite. In a base bath, ZnS is of rod structure and exists mainly in the form of sphalerite. EDS analysis indicates that a small amount of Ag is loaded on the ZnS. The sample A has mixed-crystallized structure with bigger red-shifted in UV-vis absorption spectrum, and the doped Ag is liable to separate the photo-induced e-and h+, which presents the best photocatalytic activity for H₂ production.