We demonstrate the tungsten disulfide (WS2) thin film catalysts prepared by the sulfurization of vacuum deposited WO3 thin films for efficient hydrogen production with over 90% Faradaic efficiency. The 23-nm-thick WS2 thin film catalyst heterojunction with p-type silicon photocathode could exhibit a photocurrent density of 8.3 mA/cm2 at 0 V versus a reversible hydrogen electrode (RHE), a low onset potential of 0.2 V versus RHE when photocurrent density reaches −1 mA/cm2 and long-term stability over 10 h. The enhanced catalytic activities of WS2/p-Si photocathodes compared with the bare p-Si photocathode originate from a number of edge sites in the synthesized polycrystalline thin films, which could act as hydrogen evolution catalyst.