N-oxyl compounds, in particular 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), have attracted considerable attention in alcohol oxidations due to their remarkably low-cost, high selectivity, and metal-free nature. TEMPO-mediated oxidations are often performed in high pH electrolytes as high OH - alleviates both kinetic and thermodynamic limitations. However, the degradation of TEMPO is also favorable in base, resulting in significant loss of catalytic activity and challenging long-term electrosynthesis. By contrast, ionic Liquids (ILs) possess high alkaline chemical stability. Herein, we designed electrode composites in which ILs are used as on part of a biphasic system (electrode phase and buffer phase) preserving TEMPO catalytic stability. Polycaprolactone (PCL), a binder that also possesses low melting point, was applied as a comparison. The results indicated that the IL-TEMPO composite showed no loss of current for glycerol oxidation at pH 10.0 after 2.0 h, while 67.1% current was lost using PCL-TEMPO. This stability enhancement was further evaluated in an 800 μL electrochemical cell using bulk chemical analysis and successive cycles of glycerol oxidation. The strategy demonstrated here not only offers an opportunity to prepare catalytic systems with enhanced stability, but also converts what are typically homogeneous catalysts to heterogenous systems. In subsequent studies, we aim to exploit poly(ionic liquids) (PILs) to further regulate TEMPO catalytic activity at various pH conditions. Figure 1