Li-S chemistry is regarded as promising next-generation battery technology. However, its complex redox process and long-chain lithium polysulfides shuttling are hindering the development of practical Li-S battery technology. To address these problems, many transition-metal-oxide-based catalysts have been investigated to chemically bind soluble lithium polysulfides and accelerate their redox kinetics. However, the intrinsic poor electrical conductivities of these oxides restrict their catalytic performance, consequently limiting the sulfur utilization and the rate performance of Li-S batteries. Herein, we report a freestanding electrocatalytic sulfur host consisting of hydrogen-treated VO2 nanoparticles (H-VO2) anchored on nitrogen-doped carbonized bacterial cellulose aerogels (N-CBC). The hydrogen treatment enables the formation and stabilization of the rutile VO2(R) phase with metallic conductivity at room temperature, significantly enhancing its catalytic capability compared to the as-synthesized insulative VO2(M) phase. We characterized the electrocatalytic performance of this unique H-VO2@N-CBC structure using several methods and found that the activation energy between S8 and polysulfides and the one between polysulfides and Li2S are largely reduced by 28.2 and 43.3 kJ/mol, respectively. Accordingly, the Li-S battery performance is greatly improved, with a high initial specific capacity of 1347 mAh g−1 at 0.1 C and remarkable cycling stability with a capacity of 758 mAh g-1 after 300 cycles at 1 C. This work provides an effective strategy for designing and fabricating conductive oxide catalysts to promote the electrochemical performance of Li-S batteries.