An inner coating method is developed to synthesize electrode materials for lithium ion batteries. Different from other conventional coating methods, the inner coating method employs one-dimensional (1D) conductive materials to form a three-dimensional (3D) electronic conductive and mechanical network, which can not only improve electronic and ionic conductivity, increase the reactive area, but it also accommodates volume changes associated with active materials. The concept of our inner coating method is demonstrated via the synthesis of MnO2@CNT microspheres, which uses CNT as the inner coating material. The reversible capacity increases significantly from 528.0 mAh g−1 for the MnO2 (without inner coating) to 1097.3 mAh g−1 for the MnO2@CNT (with inner coating). Cycling stability is also greatly improved via inner coating technique. This method can be extended to the synthesis of other high capacity electrode materials, which will promote the development of next-generation lithium-ion batteries.