Lithium-sulfur (Li-S) batteries are identified as one of the most promising next-generation battery technologies owing to their high theoretical specific energy, sustainability, and affordability. However, the commercialization of Li-S batteries has been hindered by severe technical challenges, including the lithium polysulfide (PS) dissolution/shuttling effect, a major cause of fast capacity degradation over cycling. We demonstrated that nanolayer polymer coated high surface area porous carbons (NPCs) were coated directly on sulfur electrodes (NPC-S), which led to a high specific capacity of ~1,600 mAh/g approaching the theoretical specific capacity limit. The NPC-S based Li-S batteries maintained their large initial specific capacity gain compared with the Baseline-S based Li-S batteries (control) over extended cycles. Our experimental and computational results suggest that NPC coated on sulfur electrodes provides not only an effective and strong PS-trapping power but also an increased redox reaction kinetics during battery charge and discharge, rendering the realization of near-theoretical discharge specific capacity in the NPC-S based Li-S batteries. The findings presented in this study may inspire a new, simple, low-cost, and commercially scalable approach, without adding any appreciable dead weight or volume to the batteries, in the effort to tackle the technical challenges facing SOA Li-S batteries.