The insulating nature of elemental sulfur has been regarded as a major challenge limiting the electrochemical performance of Li–S batteries. Consequently, previous efforts have focused on developing conductive porous materials to enhance sulfur contact. In this study, we review this conventional assumption and demonstrate that the insulating property of sulfur is not the primary factor affecting Li–S battery performance. Instead, we introduce a novel sulfur host design using polar mesoporous carbon (p-MC), which possesses ultra-low electrical conductivity (6.45 × 10−7 S cm−1) and functional groups. Our results demonstrate that all sulfur particles within the nearly insulating p-MC matrix actively participate in electrochemical reduction during the initial discharge. A comparative study with a nonpolar mesoporous carbon host, which features a similar porous structure but higher conductivity (1.07 × 10−1 S cm−1), showed that the p-MC host achieved superior cycling stability. This performance is attributed to the strong interaction between the polar functional groups of p-MC and lithium polysulfides, enabling effective and stable confinement of the active materials during cycling. Our findings highlight a paradigm shift in the design of sulfur host materials and the critical role of polar functionalities. This study offers a promising strategy for the development of durable and high-performance Li–S batteries.