A number of methods have been attempted to suppress the shuttle effect in lithium-sulfur (Li-S) batteries to improve battery performance. Conventional methods, however, reduce the ionic conductivity, sacrifice the overall energy density and increase the cost of production. Here, we report a facile synthesis of an acrylate-based hierarchical electrolyte (AHE). This quasi-solid electrolyte is assembled by in-situ gelation of a pentaerythritol tetraacrylate (PETEA)-based gel polymer electrolyte (GPE) into a polymethyl methacrylate (PMMA)-based electrospun network. The structural similarity and synergetic compatibility between the electrospun network and GPE provide the AHE an ester-rich robust structure with a high ionic conductivity of 1.02×10−3 Scm−1 due to the strong uptake ability and the elimination of commercial separator. The S/AHE/Li polymer battery also renders a high rate capability of 645mAhg−1 at 3C, while maintaining excellent retention at both high and low current densities (80.3% after 500 cycles at 0.3C and 91.9% after 500 cycles at 3C). First-principle calculations reveal that the reduced shuttle effect can be attributed to a strong polysulfide anchoring ability of ester functional groups, while cell modeling shows that the geometric design effectively suppresses polysulfide flux. This in-situ integrated method opens up an avenue for the future development of solid-state and polysulfide redox flow sulfur-based batteries.