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[Display omitted] • A multi-functional electrocatalyst of CoOOH/hollow carbon sphere (PHCS) was synthesized. • DFT calculation confirms the catalytic performance of CoOOH for Li 2 S x conversion. • DFT calculation certificates the promotion of CoOOH on OER reaction kinetic. • The CoOOH-PHCS cathode delivers satisfactory lithium storage performance. • The CoOOH-PHCS demonstrates excellent OER and ORR activity in the alkaline electrolyte. Materials with excellent electrocatalytic properties play an important role in the field of electrochemistry. In this work, a multi-function electrocatalyst of cobalt oxyhydroxide decorating homogeneous porous hollow carbon sphere (CoOOH-PHCS) was designed and fabricated. The CoOOH-PHCS can not only be used as an electrocatalyst to inhibit the shuttle effect in Li-S batteries (LSBs), but also can effectively accelerate the reaction kinetics in oxygen reduction/evolution reactions (ORR/OER). Meanwhile, density functional theory (DFT) calculations were performed to investigate the electrocatalytic activity of the CoOOH-PHCS. Benefiting from the synergy effect of CoOOH and PHCS, the CoOOH-HPC/S electrode exhibits a low capacity decay of 0.04% per cycle in 450 cycles at 1C. Meanwhile, the CoOOH-PHCS demonstrates excellent OER and ORR activity in the alkaline electrolyte. This work explores and reveals the application potential of CoOOH in electrocatalytic field. [ABSTRACT FROM AUTHOR]