Although lithium-sulfur batteries show great promise for next-generation energy storage due to their high energy density, the practical implementation of lithium-sulfur batteries has been largely impeded by the shuttle effect of lithium polysulfides and low areal capacity (< 2 mAh cm−2). Here we rationally design a new self-standing host enabled by a 3D hierarchically-porous titanium monoxide-graphene composite film to overcome the two issues at once. The hierarchically porous graphene scaffold not only can facilitate rapid lithium ion and electron transport, but also provide sufficient spaces to accommodate sulfur and buffer the volume expansion during the lithiation process. In addition, the ultrafine and polar titanium monoxide nanoparticles embedded in the three-dimensional graphene networks show strong chemical anchoring for polysulfides as evidenced by ex-situ X-ray photoelectron spectroscopy analysis, and their inherent metallic conductivity accelerates the redox reaction kinetics. Benefiting from this attractive architecture, the freestanding titanium monoxide-graphene/sulfur cathode delivered a high initial capacity of 1350 mAh g−1 at 0.1 C, a Coulombic efficiency approaching 100%, and a high-rate capacity of 832 mAh g−1 at 2 C. Moreover, when the areal sulfur loading was increased to 5.2 mg cm−2, the titanium monoxide-graphene/sulfur electrode delivered a high areal capacity of 3.2 mAh cm−2 after 300 cycles at 0.2 C, demonstrating excellent cycling performance compared with other recently reported sulfur cathodes with high areal sulfur loadings.