To boost the electrochemical performance of MnCO3 (MC) microspheres, binary SbxMn1-xCO3 (x=1/3, 1/2 and 2/3) microspheres, labeled SMC-12, SMC-11 and SMC-21, respectively, were prepared using a solvothermal method. A 3D conductive network of carbon nanotubes (CNT) was also successfully built from the inside to the surface of the SMC-12 microspheres to promote electronic and ionic transportation. As observed, the microspheres of SMC-12 were larger and had a more uniform distribution compared with pure MC, SMC-11 and SMC-21. Profiting from the introduction of neural-like CNTs networks, the electrochemical performance and the utility of the SMC-12 microspheres (approximately 3.5-7 mu m in diameter) were remarkably improved. The obtained CNTs@SMC-12 composite anode delivered 1066 and 572mAhg(-1) at current densities of 500 and 5000mAg(-1) after 200 cycles, respectively, which were much higher than the 737 and 297mAhg(-1) of bare SMC-12.Graphical abstractWith the successful construction of a 3D neural-like CNTs conductive network for the Sb1/3Mn2/3CO3 (SMC-12) microsphere, the rate performance, the cyclic stability, the utility of the large size SMC-12 microspheres are remarkably promoted. [GRAPHICS]