Discovering effective bifunctional catalysts to facilitate Li2O2 oxidation and prolong discharge life to ease batteries’ “sudden death” is a key task for developing high performance Li-O2 batteries. Herein, an advanced aprotic Li-O2 battery is designed using Co9S8@carbon porous nanocages as a bifunctional catalyst derived from a metal-organic framework. It achieves superior electrocatalytic activity, resulting in a high-energy efficiency of 72.7% and long cycle life of up to 110 cycles at 100 mA∙g−1 current density. Combined experimental studies and density functional theory calculations reveal that the promising electrochemical performance observed here could be attributed to the high catalytic activity of Co9S8. In addition, the open-framework porous structure of these carbon porous nanocages provides a facile mass transport pathway and fast charge transfer kinetics for oxygen evolution/reduction reactions