Lithium–oxygen (Li–O2) batteries are promising candidates for high-performance energy storage systems because of their tremendous energy density, which significantly exceeds that of conventional Li–ion batteries. Cobalt oxide (Co3O4) is considered an effective catalyst for non-aqueous Li-O2 batteries owing to its excellent oxygen reduction and oxygen evolution reaction activity. However, low electrical conductivity and agglomeration of Co3O4 can degrade the electrochemical performance properties. We present a facile method of synthesizing porous carbon/Co3O4 composites derived from metal–organic frameworks (MOFs) via post-thermal treatment for use as the cathode in rechargeable Li–O2 batteries. Use of cobalt-containing MOFs as a sacrificial template produces uniformly distributed Co3O4 nanoparticles in the carbonaceous matrix, alleviating the problems of using only Co3O4 as the cathode material. As-synthesized porous carbon/Co3O4 composites show superior electrochemical performance, for example, a low overpotential and high reversible capacity of about 9850mAhg−1 at a current density of 100mAg−1. They also exhibit excellent cyclability up to the 320th cycle, with a limited capacity of 500mAhg−1 at a current density of 200mAg−1. The improvement is attributed to the catalytic activity and mesoporous structure of uniformly distributed Co3O4 nanoparticles in the carbonaceous matrix.