<p>Recent advancements in Zn-halogen batteries have focused on enhancing the adsorptive or catalytic capability of host materials and stabilizing complex intermediates with electrolyte additives, while the halogen-ion electrolyte modifications exhibit strong potential for integrated interfacial regulation. Herein, we design an electrically insulating rigid electrolyte container to immobilize a liquid halogen-ion electrolyte for separator-free Zn-halogen batteries with customizable electron transfer. Robust hydrogen bonding of hydroxyl groups in SiO₂ with fluorinated moieties in PVDF-<i>hfp</i> regulates Zn²⁺ solvation and suppresses H₂O activity, while multi-channels formed by microcracks and interparticle gaps not only enhance mass transfer but also buffer interfacial electric field, jointly enabling a durable Zn plating/stripping. Effective confinement of intermediates also ensures the high reversibility across single-(I⁻/I⁰), double-(I⁻/I⁰/I⁺), and triple-(I⁻/I⁰/I⁺, Cl⁻/Cl⁰) electron transfer mechanisms at cathode, as evidenced by the double-electron transfer systems exhibiting a low capacity decay rate of 0.02‰ over 4500 cycles at 10 mA cm⁻² and a high areal capacity of 11.9 mAh cm⁻² at 2 mA cm⁻². This work presents a novel “container engineering” approach to halogen-ion electrolyte design and provides fundamental insights into the relationships between redox reversibility and reaction kinetics.</p>