We report a new method to promote the conductivities of metal–organic frameworks (MOFs) by 5 to 7 magnitudes, thus their potential in electrochemical applications can be fully revealed. This method combines the polarity and porosity advantages of MOFs with the conductive feature of conductive polymers, in this case, polypyrrole (ppy), to construct ppy‐MOF compartments for the confinement of sulfur in Li–S batteries. The performances of these ppy‐S‐in‐MOF electrodes exceed those of their MOF and ppy counterparts, especially at high charge–discharge rates. For the first time, the critical role of ion diffusion to the high rate performance was elucidated by comparing ppy‐MOF compartments with different pore geometries. The ppy‐S‐in‐PCN‐224 electrode with cross‐linked pores and tunnels stood out, with a high capacity of 670 and 440 mAh g−1 at 10.0 C after 200 and 1000 cycles, respectively, representing a new benchmark for long‐cycle performance at high rate in Li–S batteries. MOF host S: The electrical conductivity of metal–organic frameworks (MOFs) was promoted by the construction of polymer–MOF composites. Using MOF‐based sulfur hosts, the critical role of porosity at high charge–discharge rates in Li–S batteries was elucidated. MOFs with short ion transfer pathways and large pore apertures were identified as the most suitable for long‐term cycling at extremely high rates.