Despite having ultra-high theoretical specific capacity and theoretical energy density, lithium-sulfur (Li-S) batteries suffer from their low Coulombic efficiency and poor lifespan, and the commercial application of Li-S batteries is seriously hampered by the severe “shuttle effect” of lithium polysulfides (LiPSs) and the large volume expansion ratio of the sulfur electrode during cycling. Designing functional hosts for sulfur cathodes is one of the most effective ways to immobilize the LiPSs and improve the electrochemical performance of a Li-S battery. In this work, a polypyrrole (PPy)-coated anatase/bronze TiO2(TAB) heterostructure was successfully prepared and used as a sulfur host. Results showed that the porous TAB could physically adsorb and chemically interact with LiPSs during charging and discharging processes, inhibiting the LiPSs’ shuttle effect, and the TAB’s heterostructure and PPy conductive layer are conducive to the rapid transport of Li+and improve the conductivity of the electrode. By benefitting from these merits, Li-S batteries with TAB@S/PPy electrodes could deliver a high initial capacity of 1250.4 mAh g−1at 0.1 C and show an excellent cycling stability (the average capacity decay rate was 0.042% per cycle after 1000 cycles at 1 C). This work brings a new idea for the design of functional sulfur cathodes for high-performance Li-S battery.