A novel 2D-TiO2-2D van der Waals (vdW) heterostructured ([email protected]2@G) hydrogel is developed as a high-performance anode material for lithium ion batteries by coating black phosphorus nanosheets (BPNs) onto porous graphene/TiO2 composite hydrogel (TiO2@G). This unique 2D-TiO2-2D vdW heterostructure not only prevents close restack between 2D nanosheets, but also provides rapid interlayer transfer paths and enhanced interfacial storage, together with some inherited advantages from 2D BPNs and graphene, such as shortened diffusion pathways, improved conductivity, supressed volume changes and lithium dendrite growth over cycling. As a result, [email protected]2@G anode delivers an attractive initial discharge capacity as high as 1336.1 mAh g−1 (at 0.2 A g−1), a superior rate capability (271.1 mAh g−1 at 5.0 A g−1), and a good cycling life (502 mAh g−1 for 180 cycles) under a potential window close to 3.0 V. This study thus opens a new window for designing novel high-performance electrodes for electrochemical energy storage devices.