Controlling electrode/electrolyte interfacial chemistry is critically important for improved K⁺ storage, but the influences of binder chemistry on electrolyte decomposition and interfacial properties are still poorly understood. Herein, sodium carboxymethyl cellulose (CMC)-based, and polyvinylidene fluoride (PVDF)-based graphite electrodes are introduced as model systems to quantify the electrolyte decomposition, solid electrolyte interphase (SEI) formation, and the corresponding kinetic evolution transition. A noncatalytic electrolyte reduction path on the CMC-based electrode and a catalytic reduction path on the PVDF-based electrode are identified, in terms of the reduction overpotential and product selectivity. The electrolyte reduction and/or SEI formation are found to occur in a successive, two-step manner, starting with the electrochemical reduction at a potential above 0.35 V where no potassiation has happened (step I), and followed by the thermodynamically accelerated electrolyte reduction at a potential below 0.35 V (step II). Kinetics analysis reveals the former is charge transfer-controlled for both CMC and PVDF-based electrodes, and the latter involves a kinetic transition to SEI resistance controlled for the PVDF system, while it is charge transfer-controlled for the CMC system. All these examples, highlight that binder chemistry plays a dominant role in the electrolyte decomposition and electrode/electrolyte interfacial properties, and promote a better fundamental understanding of electrolyte reduction.