MoS2/montmorillonite (MoS2/MMT) composite nanosheets have been successfully synthesized by a facile hydrothermal method, and the catalytic activities of composites are evaluated by reduction reaction of methyl orange in aqueous phase. A preparation strategy demonstrates that MoS2 can be in situ formed on the surface of MMT from Na2MoO4 center dot and H2NCSNH2. The microstructures and morphologies characterization indicates that few-layered MoS2 nanosheets are uniformly grown on the surface of montmorillonite, and the hydrogen bonds are formed at the interfaces. The catalytic activity of MoS2/MMT is enhanced by support of montmorillonite, which can be attributed to the large surface area, more reactive sites, dispersibility of MoS2/MMT,and the synergistic adsorption property of montmorillonite. Based on density functional theory calculations, the preferred adsorption configurations of MoS2 cluster on MMT are studied. The supporting effect of MMT on MoS2 nanoparticles will lead to the anchoring of these reactive MoS2 nanoparticles on clay surface and enhance the absorption ability of MoS2 to the organics and meanwhile improving the catalytic properties of the MoS2/MMT composite. The MoS2/MMT composite nanosheets show prospective application to treat effectively wastewater of dyes.