TiO2 nanocrystals/graphene hybrids (TiO2-G) with ultrafine TiO2 nanocrystals (~7 nm in size) conformally coated on ultrathin graphene nanosheets (~ 2 layers thick) were successfully prepared via a facile one-pot solvothermal route under mediated conditions. With the feature of large surface area, abundant mesopores and high thermal stability, the TiO2-G nanohybrids exhibited large reversible Li-ion storage capacity with excellent cycling stability (629 mAh·g−1 after 400 cycles at a current of 60 mA·g−1) and good rate capability (184 mAh·g−1 at a current density of 3 A·g−1) due to the synergetic effects and strong interactions between the components, showing great promise in applications for advanced energy storage devices.