Herein, we introduce a novel peapod-like architectural array with TiO2 nanoparticles encapsulated in graphitized carbon fibers for the first time. The unique peapod-like TiO2 arrays with high conductivity architectures are designed and fabricated for application in Li-ion batteries. Since the as-synthesized TiO2 peapod array is characterized with the large surface area derived from the mesoporous carbon fiber, as well as the high conductivity further enhanced by a thin carbon coating layer, it has shown superior rate capability, high specific capacitances, and excellent cycling stability, e.g. the specific capacity can reach up to 162 mA h g(-1) over 200 cycles. A rational and universal approach to fabricate a high-performance TiO2 peapod array for constructing next-generation Li-ion batteries is demonstrated in this paper. Furthermore, due to the specificity of the structure and the versatility of TiO2, the nanocomposite can also be applied in photochemical catalysis, electronics, biomedicine, gas sensing and so on.