We present a design and synthesis of a hierarchical architecture of multi-walled carbon nanotubes @ mesoporous carbon (MWCNT@Meso-C) using unique multi-walled carbon nanotubes @ metal–organic framework (MWCNT@MOF-5) as both template and precursor. Active sulfur is encapsulated into the MWCNT@Meso-C matrix prepared via carbonizing MWCNT@MOF-5 polyhedrons for high performance lithium sulfur battery. The initial and 50th cycle discharge capacity of MWCNT@Meso-C/S sulfur cathode are as high as 1343 mAh g−1 and 540 mAh g−1 at a high current rate of 0.5 C. CV and EIS tests indicate that the MWCNT@Meso-C/S sulfur cathode has smaller resistance and better kinetics characteristics than that of the MWCNT@MOF-5 sulfur cathode. Test results indicate that the MWCNT@Meso-C is a promising host material for the sulfur cathode in the lithium sulfur battery applications.