Here, we report a three-layer-structured hybrid nanostructure consisting of transition metal oxide TiO2 nanoparticles sandwiched between carbonaceous polymer polyaniline (PANI) and graphene nanosheets (termed as PTG), which, by simultaneously hindering the agglomeration of TiO2 nanoparticles and enhancing the conductivity of PTG electrode, enables fast discharge and charge. It was demonstrated that the PTG exhibited improved electrochemical performance compared to pure TiO2. As a result, PTG nanocomposite is a promising anode material for highly efficient lithium ion batteries (LIBs) with fast charge/discharge rate and high enhanced cycling performance [discharge capacity of 149.8 mAh/g accompanying Coulombic efficiency of 99.19% at a current density of 5C (1000 mA/g) after 100 cycles] compared to pure TiO2. We can conclude that the concept of applying three-layer-structured graphene-based nanocomposite to electrode in LIBs may open a new area of research for the development of practical transition-metal oxide graphene-based electrodes which will be important to the progress of the LIBs science and technology.