AbstractSnO2@MoO2/carbon hollow nanospheres are successfully fabricated by coating a Mo‐polydopamine chelate precursor on SiO2@SnO2 nanospheres, with subsequent annealing and HF corrosion. In the unique nanocomposites, the external carbon layer with MoO2 nanoparticles and a SnO2 hollow inner layer as the skeleton can not only enhance electronic conductivity, but also reinforce the shell of the hollow nanocomposites while preventing the aggregation of SnO2 and MoO2 nanoparticles during intensive cycles, thus enhancing the structural integrity, rate capability and cyclic stability. In virtue of the respective roles and synergistic effects of the three nanocomponents, the unique ternary nanocomposites possess an initial discharge capacity of 1097 mAhg−1, high initial coulombic efficiency of 85 %, and good cyclic performance (725 mAhg−1 after 300 cycles) as anode nanomaterials. The structural design of the MoO2/C layer coating metal‐oxide hollow nanospheres can provide a novel synthetic approach for other hybrid energy nanomaterials with excellent properties.