Transition metal oxides have been studied as positive- and negative-electrode materials for high-energy lithium-ion batteries (LIBs). The performance of LIBs depends on the characteristics of active materials such as crystal structure, matter composition, morphologies and electrical properties because of the insertion/extraction kinetics of Li ions and electron transfer. In this study, we report the strategic synthesis methods of tailored active materials for high performance LIBs using external-stimuli responsive polymer particles. Since the three-dimensional cross-linked polymer spheres can accommodate the introduction of various metal ions and polar molecules by diffusion from the aqueous and non-aqueous solutions, the hierarchically structured hybrid metal oxide spheres can be synthesized easily. The medium pH is most important factor in determining the morphologies of metal oxide particles because the mesh size of the cross-linked polymer network and the size of the diffuse polar species depend greatly on the pH of medium. Besides, the polymer phase remains the carbon residues on the surface of primary metal oxide grains during calcination process at certain heating condition. These carbon residues can accommodate the volume variation of metal oxides reacted with lithium ions as well as increasing the electrical conductivity of electrodes. We have fabricated various kinds of transition metal oxide particles and also investigated their electrochemical performances as positive- and negative-electrodes for LIBs.