Protons tend to bond strongly with unsaturated-coordinate S element located at the edge of nano-MoS2 and are consequently reduced to H2. Therefore, increasing the active S atoms quantity will be a feasible approach to enhance hydrogen evolution. Herein we developed a porous TiO2 derived from metal organic frameworks (MOFs) as scaffold to restrict the growth and inhibit the aggregation of MoS2 nanosheets. As a result, the thickness of the prepared MoS2 nanosheets was less than 3nm (1–4 layers), with more edges and active S atoms being exposed. This few-layer MoS2-porous TiO2 exhibits a H2 evolution rate of 897.5μmolh−1g−1, which is nearly twice as much as free-stand MoS2 nanosheets and twenty times more than physical mixture of MoS2 with porous TiO2. The high performance is attributed to that more active edge sites in few-layer MoS2-porous TiO2 are exposed than pure MoS2. This work provides a new method to construct MOFs derived porous structures for controlling MoS2 to expose active sites for HER.