Major efforts are currently underway to improve both energy and power densities for electrochemical energy storage devices, which are highly subject to the electronic and ionic transport kinetics in electrodes. Adding proper conductive media into nanostructured electrodes can achieve satisfactory electronic conductivities. Consequently, the ionic transport inside electrodes becomes the rate-determining step to realize high charge/discharge rates and full storage capacity. Metal oxides are commonly used as electrode materials, where channel-like interstices can reversibly transport and accommodate ions. However, the confined size of channels produces high diffusion energy barriers, especially for large-sized ions like Na+, which leads to the poor rate performance and insufficient capacity. Aiming at enlarging the diffusion channels, we design the favorable atomic structures of vanadium/manganese oxides with incorporating hydrogen, tuning allotropic structures, and manipulating oxygen vacancies. Remarkably enhanced ionic transports are predicted for proposed structures based on DFT calculations and confirmed by experimental results.