CoCO₃ with high theoretical capacity has been considered as a candidate anode for the next generation of lithium-ion batteries (LIBs). However, the electrochemical performance of CoCO₃ itself, especially the cyclic stability at high current density, hinders its application. Herein, pure phase CoCO₃ particles with different particle and pore sizes were prepared by adjusting the solvents (diethylene glycol, ethylene glycol, and deionized water). Among them, CoCO₃ synthesized with diethylene glycol (DG-CC) as the solvent shows the best electrochemical performance owing to the smaller particle size and abundant mesoporous structure to maintain robust structural stability. A high specific capacity of 690.7 mAh/g after 1000 cycles was achieved, and an excellent capacity retention was presented. The capacity was contributed by diverse electrochemical reactions and the impedance of DG-CC under different cycles was further compared. Those results provide an important reference for the structural design and stable cycle performance of pure CoCO₃.