Abstract Li-S batteries are recognized as a promising secondary battery system because of their high energy density, low cost, and environmental friendliness. However, the development of Li-S batteries is mainly limited by issues such as electrode volume expansion, lithium polysulfide (LiPSs) shuttle, and slow redox reaction kinetics of sulfur. Here, a kind of solid-state Li-S battery with in situ solidified solid-state electrolytes (SSEs) is reported, which dramatically reduces the electrode/electrolyte interfacial impedance. In addition, electrospinning is used to fabricate a macroporous carbon nanofibers film (MP-CNFs) loaded with dispersed Co-ZrO2 nanodot electrocatalyst as the cathode host. The in-situ gel electrolyte can be easily infiltrated into the porous carbon nanofibers and contact the Co-ZrO2 catalyst, thus fully exerting its catalytic and conversion effects on LiPSs. The results indicate that solid-state Li-S batteries exhibit a high initial capacity of 795.5 mA h·g−1 and a capacity retention rate of ∼100% after 200 cycles at 1 C.