Enzyme-based catalytic systems are common bioelectrocatalysts employed in biofuel cells, as a consequence of the inherently high volumetric catalytic activity towards oxidation of biofuels. Integration of these bioelectrocatalysts with organic oxidation catalysts extends their utility by enabling significant amplification of the electrocatalytic activity, which increases the rate of electrocatalytic oxidation of readily available biofuels. However, immobilization of organocatalysts is necessary for their use in biofuel cell applications. Herein, we describe the development of a hybrid catalytic architecture consisting of MWCNTs, TEMPO-modified linear poly(ethylenimine) (TEMPO-LPEI), and an enzyme, oxalate decarboxylase (OxDC) (MWCNT/TEMPO-LPEI/OxDC) to illustrate a synergistic enhancement in the electrochemical oxidation of glycerol. Specifically, we demonstrate that immobilized MWCNT/TEMPO-LPEI/OxDc permits enhanced electrocatalytic oxidation of glycerol by allowing the organic redox polymer, TEMPO-LPEI, to catalyze the oxidation of glycerol to mesoxalate, followed by cleavage of CO₂ from mesoxalate by catalytically active MWCNTs - a crucial step in the complete oxidation of glycerol. Finally, conversion of oxalate to formate by OxDc, and subsequent oxidation of formate by TEMPO-LPEI generates CO₂ while collecting up to 14 electrons per molecule of glycerol. This results in a synergistic enhancement of up to 3.3-fold. This study illustrates the promising potential of surface-immobilized, polymer hydrogel-based hybrid multicatalytic systems, and thus offers a simple methodology for fabricating bioanodes for enzymatic fuel cells.