Traditional Li-ion batteries are encountering a technical hurdle in further increasing their energy density. Li-S batteries have been attracted increasing attention owing to the high theoretical capacity of element sulfur (S, 1672mAhg−1). Nevertheless, the insulation nature of the S element and polysulfide shuttle effect, resulting in low S utilization and poor cycling stability, are the main obstacles to widespread practical utilization of Li-S batteries. To tackle these issues, a well-designed hybrid cathode, consisted of S-infused activated carbon fiber (ACF) cloth and a thin TiO2 wrapping layer (TiO2-ACF/S), is developed in this work with the TiO2 wrapping layer as a polysulfide chemisorption layer, while the ACF cloth being a conductive network. Compared to the pure S and ACF/S cathodes, the TiO2-ACF/S hybrid cathode, with a high S loading of about 3.0mgcm−2, displays an improved initial specific capacity (915mAhg−1 at 0.2C), cycle stability (capacity retention of 77% after 100 cycles, 702mAhg−1), and rate ability (438mAhg−1 at 5C). The enhanced electrochemical performances of TiO2-ACF/S hybrid cathode are attributed to the synergistic effects from TiO2 (polysulfide chemisorption material), ACF (electronically conductive material) and S (high hosting capacity of Li ions).