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Three-electrode configurations allow targeted studies of reaction mechanisms, including charge storage in and interphase formation on electrode materials for emerging sodium-ion batteries. However, using sodium metal as a reference electrode results in spontaneous formation of electroactive soluble decomposition products in an ester-based electrolyte. These electrolyte decomposition products undergo oxidation at carbon electrodes at potentials that can be mistaken for reversible sodium (de)intercalation, thus obscuring true measurements of material properties. Keywords: Sodium-ion batteries, Electroanalytical chemistry, Electrolyte decomposition