Hierarchical mesoporous hybrid NiO–MnCo2O4 microspheres are synthesized by a robust one-pot spray pyrolysis process. The mesoporous hybrid NiO–MnCo2O4 microspheres are comprised of homogeneously dispersed nanoscaled NiO and MnCo2O4 subunits. Specific surface area of the mesoporous hybrid NiO–MnCo2O4 microspheres is determined to be 10.2m2 g−1 with dominant pore size of 25.8nm. The as-obtained material is evaluated as anode material for LIBs. The as-prepared hybrid NiO–MnCo2O4 sample demonstrate better electrochemical performances, including higher reversible capacity and superior rate capability, compared with the single-phase NiO and MnCo2O4 samples. These superior electrochemical performances should be mainly attributed to its porous microstructure characteristics and the synergistic effects between the well-dispersed NiO and MnCo2O4 nanophases. The strategy is simple and flexible, so it could be readily generalized to construct other hybrid metal oxides materials.