Uniform surface conductive layers with porous morphology-conserved MnCo2O4 microspheres are successfully synthesized, and their electrochemical performances are thoroughly investigated. It is found that the microwave-assisted hydrothermally grown MnCo2O4 using citric acid as the carbon source shows a maximum Li(+) ion lithiation/delithiation capacity of 501 mA h g(-1) at 500 mA g(-1) with stable capacity retention. Besides, the given microsphere compounds are effectively activated as air cathode catalysts in Li-O2 batteries with reduced charge overpotentials and improved cycling performance. We believe that such an affordable enhanced performance results from the appropriate quasi-hollow nature of MnCo2O4 microspheres, which can effectively mitigate the large volume change of electrodes during Li(+) migration and/or enhance the surface transport of the LiOx species in Li-air batteries. Thus, the rationally designed porous media for the improved Li(+) electrochemical reaction highlight the importance of the 3D macropores, the high specific area and uniformly overcoated conductive layer for the promising Li(+) redox reaction platforms.