As the key component of electrochemical energy storage devices, an electrode with superior ions transport pores is the important premise for high electrochemical performance. In this paper, we developed a unique solution process to prepare freestanding TiO2/graphene hydrogel electrode with tunable density and porous structures. By incorporating room temperature ionic liquids (RTILs), even upon drying, the non-volatile RTILs that remained in the gel film would preserve the efficient ion transport channels and prevent the electrode from closely stacking, to develop dense yet porous structures. As a result, the dense TiO2/graphene gel film as an electrode for lithium ion battery displayed a good gravimetric electrochemical performance and more importantly a high volumetric performance.