In the work, a facile yet efficient self-sacrifice strategy is smartly developed to scalably fabricate hierarchical mesoporous bi-component-active ZnO/ZnFe2O4 (ZZFO) sub-microcubes (SMCs) by calcination of single-resource Prussian blue analogue of Zn-3[Fe(CN)(6)](2) cubes. The hybrid ZZFO SCMs are homogeneously constructed from well-dispersed nanocrstalline ZnO and ZnFe2O4 (ZFO) subunites at the nanoscale. After selectively etching of ZnO nanodomains from the hybrid, porously assembled ZFO SMCs with integrate architecture are obtained accordingly. When evaluated as anodes for LIBs, both hybrid ZZFO and ZFO samples exhibit appealing electrochemical performance. However, the as-synthesized ZZFO SMCs demonstrate even better electrochemical Li-storage performance, including even larger initial discharge capacity and reversible capacity, higher rate behavior and better cycling performance, particularly at high rates, compared with the single ZFO, which should be attributed to its unique microstructure characteristics and striking synergistic effect between the bi-component-active, well-dispersed ZnO and ZFO nanophases. Of great significance, light is shed upon the insights into the correlation between the electrochemical Li-storage property and the structure/component of the hybrid ZZFO SMCs, thus, it is strongly envisioned that the elegant design concept of the hybrid holds great promise for the efficient synthesis of advanced yet low-cost anodes for next-generation rechargeable Li-ion batteries.