Mastery over the structure of nanoscale materials can effectively tailor and regulate their electrochemical properties, enabling improvement in both rate capability and cycling stability. We report the shape-controlled synthesis of novel mesoporous bicomponent-active ZnO/CoO hierarchical multilayered bipyramid nanoframes (HMBNFs). The as-synthesized micro/nanocrystals look like multilayered bipyramids and consist of a series of structural units with similar frames and uniform sheet branches. The use of an appropriate straight-chain monoalcohol was observed to be critical for the formation of HMBNFs. In addition, the structure of HMBNFs could be preserved only in a limited range of the precursor ratio. An extremely fast crystal growth process and an unusual transverse crystallization of the ZnCo-carbonate HMBNFs were newly discovered and proposed. By calcination of ZnCo-carbonate HMBNFs at the atmosphere of nitrogen and air, ZnO/CoO and ZnCo2O4 HMBNFs were obtained, respectively. Compared to the ZnCo2O4 HMBNFs, the ZnO/CoO HMBNFs with a uniform distribution of nanocrystal ZnO and CoO subunits exhibited enhanced electrochemical activity, including greater rate capability and longer cycling performance, when evaluated as an anode material for Li-ion batteries. The superior electrochemical performance of the ZnO/CoO HMBNFs is attributed to the unique nanostructure, bicomponent active synergy, and uniform distribution of ZnO and CoO phases at the nanoscale.