To develop commercially viable lithium–sulfur batteries, it is critical to stabilize lithium deposition and mitigate lithium polysulfide (LiPS) shuttling, while minimizing excess Li. Here, we present the loading of Li2S nanoparticles into a carbon host that has been decorated with Co9S8 and Co (Li2S–Co9S8/Co) through a simple carbothermal reaction. The Co9S8/Co electrocatalyst functions as nucleation sites to ensure that Li2S is distributed uniformly throughout the composite. The molecular-level mixing of Li2S and the electrocatalyst provides a high level of catalytic activity toward Li–S redox to improve Li2S utilization and mitigate LiPS shuttling, which prevents the accumulation of large amounts of inactive Li2S on the Li anode, thus ensuring efficient utilization of Li in the cell. Benefiting from this rational design, a high capacity of 969 mA h g–1 is achieved in an anode-free cell with the Li2S–Co9S8/Co cathode. This work paves the way for the development of low-cost cathodes for anode-free Li–S batteries.