Aqueous rechargeable zinc-iodine batteries (ZIBs) are promising candidates for grid energy storage because they are safe and low-cost and have high energy density. However, the shuttling of highly soluble triiodide ions severely limits the device's Coulombic efficiency. Herein, we demonstrate for the first time a double-layered cathode configuration with a conductive layer (CL) coupled with an adsorptive layer (AL) for ZIBs. This unique cathode structure enables the formation and reduction of adsorbed I3- ions at the CL/AL interface, successfully suppressing triiodide ion shuttling. A prototypical ZIB using a carbon cloth as the CL and a polypyrrole layer as the AL simultaneously achieves outstanding Coulombic efficiency (up to 95.6%) and voltage efficiency (up to 91.3%) in the aqueous ZnI2 electrolyte even at high-rate intermittent charging/discharging, without the need of ion selective membranes. These findings provide new insights to the design and fabrication of ZIBs and other batteries based on conversion reactions.