We have developed a general methodology to realize surface coating and encapsulation of electrode materials in hierarchical graphite-like carbon matrix and studied how the composition of the copolymer (as the precursor of the graphite-like carbon) and pyrolysis temperature affect the performance of the electrode material. The typical anode material, anatase TiO2, has been used as an example to have encapsulated and distributed the TiO2 nanoparticles in the poly (acrylonitrile-co-styrene) matrix to form hybrid spheres (HSs) Then, the HSs are converted to TiO2/carbon anode materials after appropriate pyrolysis. The copolymers with different ratios of acrylonitrile to styrene from 3:7 to 5:5 have been synthesized, and the pyrolysis is performed in the temperature range from 550 to 850 degrees C. It is found that both the composition of the copolymer and the pyrolysis temperature can strongly affect the performances of the final TiO2/C anode materials. A proper design optimization is necessary to obtain the electrode materials with the desired performance. Under the optimized conditions, the capacity of the cell with the synthesized TiO2/C as the anode and Li as the reference has reached above 200mAhg(-1) at a current density of 500 mAg(-1) and stays stably around 170 mAhg(-1) after 1000 cycles.