We present a design and synthesis of a hierarchical architecture of graphene oxide @ mesoporous carbon (GO@Meso-C) using graphene oxide @ metal-organic framework hybrid materials (GO@MOF-5) as both the template and precursor. Active sulfur is encapsulated into the GO@Meso-C matrix prepared via carbonize GO@MOF-5 polyhedrons for high performance lithium sulfur battery. The initial and 100th cycle discharge capacity of GO@Meso-C/S sulfur cathode are as high as 1122 mAh g−1 and 820 mAh g−1 at a current rate of 0.2C. The remarkably high special capacity and capacity retention rate indicate that the GO@Meso-C is a promising host material for the sulfur cathode in the lithium sulfur battery applications.