Prussian Blue analogue (PBA) metal–organic frameworks (MOFs) have recently emerged as promising materials for next-generation memristive devices due to their open-framework structure, rich redox chemistry, and coupled ionic–electronic transport properties. Although resistive switching has been increasingly reported in PBAs, the fundamental mechanisms governing the switching process are still not fully understood. In this work, we demonstrate that potassium-ion intercalation is the primary mechanism responsible for the resistive switching behavior of electrodeposited PBA-MOF thin films. The reversible migration of K⁺ ions within the porous crystalline framework induces local redox changes at the transition-metal centers, dynamically modulating the electronic conduction pathways and enabling reversible transitions between high- and low-resistance states. Based on these findings, we introduce the concept of a well-controlled Chemical-Bit switching mechanism, where information storage is governed not only by electronic transport, but also by coupled ionic, electrochemical, and redox processes occurring throughout the crystalline framework. In this mechanism, the resistive state is chemically encoded through reversible ion-intercalation-induced modifications of the local electronic structure. Unlike conventional oxide-based ReRAM technologies, which typically rely on stochastic conductive filament formation and localized dielectric breakdown, resistive switching in PBA-MOFs originates from controlled ionic–electronic interactions distributed across the open framework. This switching paradigm provides a promising strategy to address the three major challenges of ReRAM technologies: reliability, endurance, and retention. The highly reversible nature of the ion-intercalation process can reduce cycle-to-cycle variability, minimize irreversible structural degradation, and stabilize the stored resistance states through controlled electrochemical transformations. Beyond the fundamental insights into the switching mechanism, electrodeposited PBA-MOFs represent a highly promising materials platform for future memory technologies due to their solution-based processability, room-temperature synthesis, low fabrication cost, and compatibility with large-area and flexible electronics. In addition, PBAs are composed of earth-abundant and environmentally benign elements, making them attractive for sustainable and scalable device manufacturing.