In this work, we investigate the interplay between mesoporous carbon (MC) and various nanomaterials to effectively host and utilize sulfur in lithium-sulfur (Li-S) batteries, particularly under high-rate conditions. Sulfur-infused MC, combined with a binder and conductive graphenic materials including graphene nanoribbons (GNRs) and reduced graphene oxide (rGO) microsheets, is deposited onto the current collector via an air-controlled electrospray process. Structural and electrochemical characterizations indicate that the pseudo-one-dimensional, partially unzipped structure of GNRs facilitates the formation of interconnected conductive networks and introduces additional pore structures, thereby enhancing charge transport. The rate-capability tests show that with 75 wt% of graphene-based materials as GNRs, the capacity of batteries reaches 480 mAh/g at 5C-rate, which is 2.3 times higher than the system without GNR. As a result, systems incorporating GNRs exhibit significantly improved rate capability compared to those using rGO and precursor carbon nanotubes (CNTs), highlighting the importance of GNR-based hybrid architectures. To further understand the intrinsic origin of this enhancement, density functional theory (DFT) simulations are performed to examine lithium-ion diffusion on different carbon structures. The results show that partially unzipped GNRs possess reduced activation energy barriers for lithium diffusion compared to planar graphene and CNTs. This improvement is attributed to the increased density of active edge sites, which provide energetically favorable pathways for ion transport, thereby contributing to enhanced high-rate performance. In addition, iron-based catalytic components, including Fe₃O₄ and Fe-NC, are incorporated into MC cathodes to further improve electrochemical performance. Iron oxides and carbides derived from thermal treatment reduce charge-transfer resistance and enhance rate capability, although certain synthesis conditions may introduce irreversible side reactions during initial cycling. Optimization of thermal processing mitigates these effects while maintaining improved performance. Furthermore, Fe₃O₄ demonstrates strong interactions with polysulfides, effectively suppressing the shuttle effect. In parallel, nitrogen doped carbon species (NC) is introduced into iron-based catalyst (Fe-NC) and incorporated into MC. Fe-NC catalysts introduce Fe-Nₓ active sites that accelerate polysulfide conversion without inducing side reactions associated with high-temperature synthesis. This leads to enhanced reaction kinetics and stable high-rate performance. Overall, this study demonstrates that the integration of graphene-based conductive networks and iron-based catalytic materials provides a promising strategy for developing high-performance Li-S batteries with improved rate capability and stability.