Lithium-sulfur (Li-S) batteries have emerged as a promising alternative energy storage system due to their high energy density and cost-effectiveness. However, practical applications of Li-S batteries are hindered by challenges such as the shuttle effect and sluggish redox kinetics. In this study, a three-dimensional (3D) flower-like diaminoanthraquinone (DAAQ)-covalent organic framework (COF) was developed, featuring nanorod-like petals and enriched with abundant N and O adsorption sites, serving as a host material for the sulfur cathode of Li-S batteries. Through a process of sulfur melting-diffusion, the resulting DAAQ-COF@S cathode material demonstrated a stable 3D cross-linked morphology with a hierarchical pore structure, maximizing the exposure of N/O adsorptive sites and facilitating rapid ion diffusion. This effectively inhibited the shuttling effect of lithium polysulfides (LiPSs) and enhanced rate performance. Consequently, DAAQ-COF@S cathodes exhibited a high initial discharge capacity of 1182.0 mAh g−1 at 0.1 C, with a capacity retention rate of 79.6% after 500 cycles at 2 C. Even at a high current density of 4 C, they maintained a high capacity of 616.8 mAh g−1, surpassing the majority of previously reported COF-based host materials for Li-S batteries. This work underscores the significance of COF micromorphology and advances the development of high-performance cathodes for Li-S batteries.