Low-cost, safe, and environmental-friendly rechargeable aqueous zinc-ion batteries (ZIBs) are promising as next-generation energy storage devices for wearable electronics among other applications. However, sluggish ionic transport kinetics and the unstable electrode structure during ionic insertion/extraction hamper their deployment. Herein, a new cathode material based on a layered metal chalcogenide (LMC), bismuth telluride (Bi2Te3), coated with polypyrrole (PPy) is proposed. Taking advantage of the PPy coating, the Bi2Te3@PPy composite presents strong ionic absorption affinity, high oxidation resistance, and high structural stability. The ZIBs based on Bi2Te3@PPy cathodes exhibit high capacities and ultra-long lifespans of over 5000 cycles. They also present outstanding stability even under bending. In addition, here the reaction mechanism is analyzed using in situ X-ray diffraction, X-ray photoelectron spectroscopy, and computational tools and it is demonstrated that, in the aqueous system, Zn2+ is not inserted into the cathode as previously assumed. In contrast, proton charge storage dominates the process. Overall, this work not only shows the great potential of LMCs as ZIB cathode materials and the advantages of PPy coating, but also clarifies the charge/discharge mechanism in rechargeable ZIBs based on LMCs.