Novel hierarchical porous SnO2/Mn2O3 core-shell microspheres (SMCM) are successfully prepared by wet chemistry method to grow SnO2 shell on the pre-obtained Mn2O3 microsphere core. As a result, these SnO2/Mn2O3 core-shell microspheres exhibit superior electrochemical performances as the advanced anode materials. Especially, the porous SnO2/Mn2O3 core-shell microspheres could exhibit high initial discharge capacity of 1365 mA h g−1 and maintain a reversible capacity of 486 mA h g−1 even after 400 cycles at 200 mA g−1. The unique structural features of the porous, quasi-hollow structure comprised of interconnected nano-sized particles and the peculiar synergistic effect of SnO2/Mn2O3 are probably responsible for the enhanced performance.