Al–S battery (ASB) is a promising energy storage device, notable for its safety, crustal abundance, and high theoretical energy density. However, its development faces challenges due to slow reaction kinetics and poor reversibility. The creation of a multifunctional cathode material that can both adsorb polysulfides and accelerate their conversion is key to advancing ASB. Herein, a composite composed of polyoxometalate nanohybridization-derived Mo₂C and N-doped carbon nanotube-interwoven polyhedrons (Co/Mo₂C@NCNHP) is proposed for the first time as an electrochemical catalyst in the sulfur cathode. This composite improves the utilization and conductivity of sulfur within the cathode. DFT calculations and experimental results indicate that Co enables the chemisorption of polysulfides while Mo₂C catalyzes the reduction reaction of long-chain polysulfides. X-ray photoelectron spectroscopy (XPS) and in situ UV analysis reveal the different intermediates of Al polysulfide species in Co/Mo₂C@NCNHP during discharging/charging. As a cathode material for ASB, Co/Mo₂C@NCNHP@S composite can deliver a discharge-charge voltage hysteresis of 0.75 V with a specific capacity of 370 mAh g⁻¹ after 200 cycles at 1A g⁻¹.