Metal-organic-foams (MOFs)-derived nanostructures have received broad attention for secondary batteries. However, common strategies are focusing on the preparation of dispersive materials, which need complicated steps and some additives for making electrodes of batteries. Here, we develop a novel free-standing Co9S8 polyhedron array derived from ZIF-67, which grows on a three-dimensional carbon cloth for lithium-sulfur (Li-S) battery. The polar Co9S8 provides strong chemical binding to immobilize polysulfides, which enables efficiently suppressing of the shuttle effect. The free-standing S@Co9S8 polyhedron array-based cathode exhibits ultrahigh capacity of 1079 mAh g-1 after cycling 100 times at 0.1C, and long cycling life of 500 cycles at 1C, recoverable rate-performance and good temperature tolerance. Furthermore, the adsorption energies towards polysulfides are investigated by using density functional theory (DFT) calculations, which display a strong binding with polysulfides.